1

PH 3001: QUANTUM MECHANICS I (45L, 3C)

Dependencies: PH 1001 is recommended
Syllabus: Inadequacies of classical physics and evolution of quantum physics; Particles and wave
packets; Heisenberg uncertainty principle and its consequences, some illustrations of uncertainty
principle; Wave function and its interpretation, position probability density, superposition principle;
Time-dependent Schrodinger equation; Conservation of probability, probability current density;
Dirac bracket notation; Linear operators and their properties: eigenvalues and eigenfunctions of
operators, Hermitian operators, adjoint operator; Expansions in eigenfunctions: Orthogonality,
degeneracy, probability amplitudes, discrete and continuous spectra; Commutators, commuting
observables, compatibility; Expectation values; Time-independent Schrodinger equation, stationary
states; Energy quantisation; Properties of the energy eigenfunctions; General solution of the timedependent Schrodinger equation; Solutions of the time-independent Schrodinger equation for a
particle moving in a region of zero potential, step potential, barrier potential, finite square well
potential, infinite square well potential, linear harmonic oscillator potential and square box
potential; Symmetry and parity; One-electron atoms: separation of the time-independent
Schrodinger equation in spherical polar co-ordinates, energy levels, quantum numbers, degeneracy,
eigenfunctions of the bound states, probability densities; Orbital angular momentum and orbital
magnetic dipole moment of electron; Stern-Gerlach experiment, existence of spatial quantisation,
spin angular momentum and spin magnetic dipole moment of electron; Spin-orbit interaction; Total
angular momentum; Spin-orbit interaction energy and the hydrogen energy levels; Transition rates
and selection rules
Assessment: Mid & End of semester written examinations
References: Quantum Physics R. Eisberg and R. Resnick
Quantum Physics S. Gasiorowicz
Quantum Physics M.S. Rogalski and S.B. Palmer
Introduction to Quantum Mechanics B.H. Bransden and C.J. Joachain
Quantum Mechanics R.L.Liboff
Introduction to Quantum Mechanics D.J. Griffiths

Introduction:
Transition from classical to quantum theory was required mainly due to experimental findings during
the period from late 1800s to early 1900, such as

the interaction of electromagnetic radiation with matter was not entirely according to the laws
of electromagnetism as developed by Ampere, Laplace, Henry, Maxwell, etc

the development of the theory of atomic structure of matter, as a result of the discovery of the
electron and the confirmation of the nuclear model of the atom

the deviation of the experimentally measured motion of subatomic particles from what was
predicted under the assumptions of Newtonian mechanics.

2
To explain the new observations, what is known today as the "Quantum Theory" was developed. In
this course we will first briefly review the phenomena which forced physicists to introduce the new
concepts: the particle properties of radiation, the wave properties of matter and the quantization of
physical quantities, which led to the transition from classical to quantum theory. Simply speaking,
quantum theory (or quantum mechanics) is a physical science that deals with the behavior of matter
and energy on the scale of atoms and subatomic particles/waves.
Blackbody radiation and Planck's hypothesis (Birth of Quantum Physics)
Blackbody: A surface that totally absorbs all the radiation falling on it.

E ( ) - Monochromatic energy density (Spectral Distribution Function).

E()
Rayleigh-Jeans formula
Wein formula

Planck formula

Max Planck (in 1900) derived=

the expression E ( )

(8 hv

) (

/ c3 1 eh

kT

1 using the following

model for the radiating atoms.

* Each atom behaves as a harmonic oscillator oscillating with some frequency .
* Each oscillator can absorb or emit radiation energy only in an amount E = h .
(The classical e/m theory permits a continuous absorption of energy of an oscillator (amplitude)2).
The possible (quantized) values of the energy of an oscillator, En = nh , where n = 1, 2, 3, .
Planck's expression agreed well with experimental values of E ( ) at different temperatures. However, it was
not compelling enough for the conclusion of the quantum (particle) nature of radiation.

Photoelectric Emission - ejection of electrons from a surface by the action of light (Heinrich Hertz, 1887)
Irradiation of certain metals with visible and ultraviolet light showed that,
1. the photoelectron current, when exists, increases with an increase in the intensity of the incident
radiation.
2.

for each substance, there is a minimum (threshold) frequency of the e/m radiation such that below
which no matter how intense the radiation, no photoelectrons are produced.

3
3. the kinetic energy of the photoelectrons is independent of the intensity of the light source but varies
linearly with the frequency of the incident radiation.
4. the time delay between the irradiation and the emission ~ 109 s (in classical theory) but it is <<<
109 s in actual observation.
P.e. effect could not be explained using only classical theories. In 1905, Albert Einstein considered the radiation
to consist of a collection of quanta of energy (particle nature of radiation) and proposed that the energy absorbed
by an electron in a single process (in a time <<< 109 s) from e/m radiation of frequency is h .

Then, if is the energy required by a photoelectron to escape from a metal by overcoming the
Coulomb potential barrier, the kinetic energy of the escaping electron is

Ek = h

The value of does not depend on the electron energy and its value is not the same for all electrons in the
metal. The minimum value of (= 0 ) is called the work function of the metal.
There is a minimum value of (= 0 ) such that

h 0 0 =
0

( Ek )max

=
h 0

0 = 0 h

0 is called the threshold frequency for photoemission.

In the photon picture (particle nature) of radiation, the intensity is proportional to the number of photons
per unit area per unit time
The photo current is proportional to the source intensity (explains the 1st observation)

When < 0

Ek

( Ek )max

< 0 No photoelectric emission (explains the 2nd observation)

= h Ek (explains the 3rd observation)

An important contribution to the acceptance of the quantum nature of radiation came from the theoretical
work of Einstein for explaining the photoelectric effect

The Compton Effect - Scattering of radiation by free electrons (Arthur Compton in early 1920s)
It provided the most direct evidence for the particle nature of radiation. When e/m radiation of wavelength 0
was scattered by free electrons through a given angle, the scattered beam consisted of two components, one with
the wavelength 0 and the other with a wavelength shifted relative to 0 by an amount that depends on the
scattering angle. This was not consistent with classical radiation theory, according to which the incident
radiation should be re-radiated by electrons and the intensity observed at an angle should vary as

(1 + cos 2 ) , independent of the wavelength of the incident radiation. Compton explained the modified
component by treating the incoming radiation as a beam of photons of energy h 0 , with individual photons
scattering elastically off individual electrons.

(In an elastic collision, both momentum and energy are

conserved.)
By interpreting the above as a collision between the electron and a particle of zero rest mass called a photon

Scattered photon
Incident Photon

For a photon,

Electron

E
= h= hc

Recoiled electron

=
p E=
c h

0
(energy, E = hc 0 and momentum, p = h 0 ), Compton showed that =

(h

me c ) (1 cos ) ,

is the photon scattering angle, C = h me c - Compton wavelength of the electron.

The measurements of the modified component agreed very well with the values predicted by the above theory.

The Balmer series

In 1895, Balmer found an empirical formula which represents the wavelength of lines in the visible and near UV
regions in the line spectrum of atomic hydrogen.
The nine lines known at that time were found to satisfy the=
formula C n 2

(n

4 , where C = 3646 ,

n = 3, 4, 5, .. for the H , H , H , ............ lines.

The existence of atomic line spectra which exhibit regularities could not be explained by the atomic models
based on classical physics. Then, N. Bohr explained this by introducing the quantum concept into the physics of
atoms.

The Bohr Model of the Hydrogen Atom

Thomson model of the atom :- electrons are embedded in a continuous distribution of positive charge.
Scattering of -particles by thin foils (Geiger and Marsden in 1908) showed occasional large angle scattering (1
in 10000).
Rutherford's nuclear model of the atom in 1911:- all of the positive charge and most of the mass of the atom are
concentrated in a region (the nucleus ~ 1014 m) that is small compared with the dimensions of the atom (~ 1010
m).
This model explained -particle scattering quantitatively. However it could not account for the spectra of
radiation from atoms and the stabilising mechanism for atoms. Rutherford's model requires the electrons to
travel in planetary orbits about the nucleus. According to e/m theory, when a charged particle is accelerating in
a circular orbit its energy is lost as e/m radiation at a rate q 2 a 2 6 0 c3 . Then, in a time of the order of 1010 s,
the electron should spiral into the nucleus resulting in a collapse of the atom.

5
To overcome the above two difficulties, N. Bohr in 1913 assumed circular orbits for electrons and only a certain
set of stable orbits (stationary states) are allowed in contrast to the infinite number of orbits possible in classical
mechanics. His model was based on the two postulates.
(i) An electron in a stable orbit does not radiate e/m energy and radiation can only take place when a
transition is made between the allowed energy levels, Eb Ea =
h ab .
(ii) The magnitude of the orbital angular momentum of the electron moving in a circular orbit around the
nucleus can take on the values L = n , where n = 1, 2, 3, ...
Assuming circular orbits for electrons and if the nuclear charge of a one-electron (hydrogen-like) atom is + Ze ,
and the radius of the orbit is r , by equating the Coulomb force with the centripetal force acting on the electron
Ze 2 4 0 r 2 = me v 2 r .
From Bohr's 2nd postulate,
=
L m=
n , we get v = Ze 2 (4 0 ) n and r = (4 0 ) 2 n 2 Zme e 2 .
e vr
The total energy of the electron En =
me v 2 2 Ze 2 (4 0 )r =
me Z 2 e 4 2 2 (4 0 ) 2 n 2 .
Note: As n

n - principal quantum number.

En 0 .
n = 1 - Ground state (K shell), n = 2, 3, 4, .... - Excited states (L, M, N, .... shells)
This discrete set of allowed electron energy levels explained the existence of regularities in atomic line spectra.
However, the Bohr model could not account for the lines in emission spectra of many-electron atoms, the
difference in their intensities and splitting in some of the lines.
Correspondence Principle: The limiting cases of quantum mechanical results are the classical physics results. The limit is reached when the
quantum numbers are large. Ex: - Show that the above principle is satisfied by Bohr atomic model.
Consider the frequency emitted when an electron makes a transition from the orbit with quantum number n to
the orbit with quantum number n 1 , when n is large.
Classically, an electron moving in a circular orbit with velocity v would emit a radiation of frequency
2

=
cl =
2 r (me 2 3 )( Ze 2 4 0 ) (1 n3 ) .
According to the Bohr model, the frequency of the emitted radiation
2

= ( En En1 ) / h = (me 4 3 )( Ze2 4 0 ) 1 (n 1)2 1 n 2 .

When n >> 1, we have 1 (n 1) 2 1 n 2 2 n3 and therefore cl .

Stationary States and their Experimental Evidence by Frank & Hertz Experiment (in 1914)
To explain the discrete (well-defined) frequency spectrum of atomic systems, Bohr assumed that the energy of
an atom can have only certain values (levels) E1 , E2 , E3 .......
corresponding to these energies are called stationary states.

- quantization of energy. The states

6
E5
E4
E3

E2

E1
Emission

Absorption

h i j + A( Ei ) A( E j )
Conservation of energy

A( E j ) A( Ei ) + h ji
h=
E j Ei and h=
E j Ei , and hence the frequencies which
ji
ij

constitute the absorption spectrum ( i j ) are the same as those observed emission spectrum ( ji ) of the system.
Consider the inelastic collision experiment (a part of the kinetic energy of the projectile is transferred as internal
energy to the target) between electrons and mercury atoms.

AG ( E1 ) + q fast

A* ( E2 ) + qslow ,

(energy transferred to the target = E2 E1 )

Let, E1 - ground state energy, E2 - first excited state energy, Ek =

1 2
mv - kinetic energy of the fast projectile
2

before collision, (Assume that, mass of the atom >> mass of the projectile no recoiling of the atom.)

Ek < E2 E1 Collision is all elastic and the electron moves through the vapour, losing energy very slowly.
Ek ~ E2 E1 Collision is inelastic, the electron may lose ( E2 E1 ) amount of energy in a single
encounter and the atom is excited to the first excited state. [k.e. of the projectile after the
collision, Ek =Ek ( E2 E1 ) ]. After exciting an atom, the energy is insufficient to
excite the other atoms and the electron may undergo elastic collisions.

E k >> E 2 E1 It may suffer few more inelastic collisions, losing the energy ( E2 E1 ) at each collision
and producing more excited atoms. (It is also possible to excite an atom to the second
excited state from the ground state)
In their experimental arrangement, a heated filament (F) emits electrons which are accelerated towards the grid
(G) by a variable potential V. The space between F and G is filled with mercury vapour. Between G and the
collecting plate P, a small retarding potential V / (~ 0.5 V) is applied so that those electrons which are left with
very little k.e. after one or more inelastic collisions can not reach the plate and are not registered by the
galvanometer. As V is increased the plate current I fluctuates with peaks occurring at a spacing of about 4.9 V.

7
The first dip corresponds to electrons that lose all their k.e. after one inelastic collision with a Hg atom, which is
then left in an excited state. The second dip corresponds to those electrons that suffered two inelastic collisions
with two Hg atoms, losing all their k.e. and so on. The excited Hg atoms return to their ground state by emitting

4.9 V

Galvanometer

V / ~ 0.5 V

10

15

V
a photon ( Hg* Hg + h , with

h=

E2 E1 ) of wavelength 2536 (corresponding to

h = 4.86 eV ), which has been observed spectroscopically as coming from the Hg vapour during the
passage of the electron beam. This experiment is one of the most striking proofs of the existence of stationary
states.
Particles and Fields
The objects we touch and see have a well-defined shape and size and therefore localized in space. When the
above picture is used for fundamental particles (eg:- e, p, n, etc) as having shape and size (as well as mass and
charge) we get into a difficulty in explaining certain experimental results.
To describe the motion of fundamental particles, Louis de Broglie (in 1924) proposed to associate a matter field
(wave) with each particle which describes the dynamical condition (momentum and energy) of the particle. [In
reverse, Planck had associated a particle (a photon) having precise momentum and energy with an e/m field.]
De Broglie assumed that the nature is symmetric and = h p can be applied to material particles as well as to
photons.
The wavelength and frequency of the matter wave associated with a particle of momentum p and energy

E are given by = h p and = E h .

Wave

number,

- de Broglie wavelength

k = 2 , angular frequency

= 2

p = k

and

E = , where

=
h=
2 1.0544 1034 J.s .
If the above assumption is correct, whenever the motion of a particle is disturbed so that the matter wave
associated with it can not propagate freely, interference and diffraction phenomena should be observed as in the
case of e/m waves.
When the electrons are accelerated by a potential V , the gain in kinetic energy

eV = p 2 2me

8
De Broglie wavelength, =
h=
p h
For V ~ 104 V

= 1.23 109
2me eV

V m

~ 1012 m ~ wavelength of X-rays (e/m waves)

i.e. if one sends a beam of fast electrons through a crystal, he should obtain diffraction patterns resulting from
matter waves similar to those obtained for X-rays (by Bragg and others).

Detector

Incident electron
beam

Diffracted
electron beam

Crystal
Davison and Germer carried out an experiment similar to one that Bragg did to observe X-ray diffraction, with
the X-ray beam replaced by an accelerated electron beam. They found that the electron current registered by the
detector was a maximum every time the Bragg condition, 2d sin = n , derived for X-rays was satisfied.
Particles and Wave Packets
Consider a free particle moving along the x-axis with a precisely known momentum p ( p x ) and
energy E = p 2 2m . As the matter wave of this particle, one can associate a harmonic wave with w.l.

= h p and freq. = E h

( x,=
t)

- Instantaneous value of the matter wave,

A sin 2 ( x =
t)

A sin(kx =
t)

Aei( k x t ) .

A amplitude, (k k x )
2

Prob. of finding the particle within a unit distance at a given place and time, =

A = Constant .

Position of the particle on the x-axis (from to +) is completely unknown, i.e. localization is not possible
for a free particle of well-defined (precisely known) momentum.
So, the harmonic wave represents the idealized situation of a particle of precisely known momentum moving
somewhere in a beam of infinite length.
The phase (or wave) velocity of the de Broglie wave, v=
p

=
k
= ( E h)(h =
p) E p

If v is the non-relativistic velocity of the particle, E = mv 2 2 , p = mv =

v p v 2 particle velocity.
Now, consider a particle localized within a certain region x of space. Then, the amplitude of its associated
matter wave should be large in that region and very small outside it. Such a wave can be formed by
superimposing (through interference) an infinite number of harmonic matter waves, each with infinitesimally
differing and k (or and ) values. Then, the amplitude of the wave is modulated so that its value is nonzero only over a finite region of space, in the vicinity of the particle. Such a superposition will result in a group
of waves or wave packet.

Vg

x
Continuous
wave
train
corresponding to an unlocalized
particle

Wave packet of extension x

corresponding to a particle
localized within the distance x

The (group) velocity of propagation of the packet, vg= d dk= dE dp=

p m= v= particle velocity (since

p = k , E = and E = p 2 2m )
The group must move with the same velocity as the particle, along the x-axis.

Note: One cannot measure the phase velocity of a pure harmonic wave directly and can only measure the group
velocity of the waves.
Consider a superimposition of two harmonic waves (the simplest case) of equal amplitudes and slightly different
frequencies and wavelengths.

1 ( x, t )=

A sin(kx t )

2 (=
x, t )

A sin ( (k + dk ) x ( + d )t )

Their resultant, ( x, t ) = 1 ( x, t ) + 2 ( x, t ) = 2 A cos[(dk 2) x (d 2)t ]sin(kx t )

(since d 2 and dk 2k ) and its amplitude has been modulated to form a group.
The second term of is a wave of the same form as 1 but is modulated by the first term so that its
oscillations fall within an envelope of periodically varying amplitude.

( x, t )
2 =
k

t=0

2
dk

10
Velocity of an individual wave is given by sin(kx t ) as =
v p =
k 2 (2 ) =
Velocity of the group is given by cos[(dk 2) x (d
=
=
2) (dk 2) d dk
2)t ] as vg (d
For the group of matter waves associated with the particle, vg= dE dp=

p m= v= particle velocity

Heisenberg's Uncertainty Principle for Position and Momentum

Consider the wave packet (group of waves) associated with a particle, with an extension ~ x , range
of wave numbers of interfering waves ~ k x .
From Fourier analysis, it can be shown that
p x = k x

x.px 2

x.k x 12 .

[Derivation is not necessary]

Heisenberg Uncertainty Principle

Similar relationships can be written for particle motion in y- and z- directions.

Other acceptable forms of writing the H.U.P.

x.px

x.px ~

x.px

x.px ~ h

Physical interpretation
If a particle is within the region x 12 x and x + 12 x (where x is the uncertainty in the position),
its associated wave packet is represented by superposing waves of momenta between px 12 px and

px + 12 px (where px is the uncertainty in the momentum) so that x.px 2 .

OR

The

relationship

x.px 2

implies

that,

as

x 0 px

and,

as

px 0 x . i.e., if we have a very precise knowledge of the position/the linear

momentum of the particle, then we have a very imprecise measurement of its linear momentum/the
position. Furthermore, as we cannot make x= 0, px= 0 at the same time, it is not possible to
measure both position and momentum in that direction of a particle exactly at the same time.
The restriction by the u.p. applies only to complementary pairs ( x, px ) , ( y, p y ) and ( z , pz ) . The
restriction does not apply to other pairs ( x, p y ) , ( y, px ) , ( z , px ) etc.,
i.e. x.p y =0 , y.px =0 , z.px =0 etc.
Note: If (or h) were zero, there would be no limitation in our simultaneous measurements of x and
px -- Classical view.
Since h is very small, we do not notice the importance of H.U.P. in our ordinary experience.

11
Eg.: The speed of a bullet (m = 50 g) and the speed of an electron (m = 9.1 1031 kg) are measured to
be the same, 300 ms1 with uncertainty of 0.01%. With what fundamental accuracy could we
have located the position of each particle, if the position is measured simultaneously with the
speed in this experiment?
For the bullet (macroscopic object),
px = mvx = 0.05 kg 300 m s1 = 15 kg m s1

vx
100=
vx

0.01 v=
x

px = mvx = m
HUP x

0.01
vx
100

0.01
0.01
0.01
vx = mvx
= 15 kg m s 1
= 1.5 103 kg m s 1
100
100
100

6.6 1034 J.s

=
= 3 1032 m = 1017 Diameter of a nucleus

1
2 px
4 1.5 10 kg m s

So, the HUP sets no practical limit to our measurement. Uncertainties of this order are always masked
by experimental errors.
For the electron (microscopic object)
px = mvx = 9.1 1031 kg 300 ms1 = 2.7 1028 kg m s1

vx
100=
vx

0.01 v=
x

0.01
vx
100

0.01
0.01
0.01
vx = mvx
=
=
2.7 1028 kg m s 1
2.7 1032 kg m s 1
100
100
100
6.6 1034 J.s

1
=
= 2 103 m = 0.2 cm = 107 Diameter of an atom
HUP x
2 px
4 2.7 1032 kg m s 1

px = mvx = m

So, the electron may be found anywhere between 1 107 atoms.

HUP sets a practical limit to our measurement.

If h ~ 6.6 104 J s, then for the bullet, x = 3 102 m = 3 cm

HUP sets a practical limit to our measurement.

As we know, for the u.p. x.px 2 to play a significant role in simultaneous measurements of x
and px , the product x.px should take a value of the order of ~ 1034 J s which is very small. In
our ordinary experiences, we have to deal with macroscopic objects, which involve significantly
large values of x and px . Therefore, even with the best measuring techniques available, we get
relatively large values for experimental uncertainties of x and px in our measurements and they will
obviously satisfy the u.p. On the other hand, when any of these values (say for x ) is substituted in
the above relation, the resulting value of px becomes so small. Since experimental uncertainties are
very much larger than the values predicted by the u.p., it sets no practical limit (with regard to
uncertainties) in simultaneous measurements of x and px . So, the effect of the u.p. is hardly
noticeable in our day-to-day life, which is not the case when dealing with microscopic objects.

12

The uncertainty relation for time and energy

( x, t )

( x, t )
t=0

x=0
x

t
Time duration

Consider the wave packet associated with a particle.

Frequency width of waves

Time duration of the group of waves

From Fourier analysis, it can be shown that, t. 1 2 (Derivation is not necessary).

E =

E.t 2

Time-energy uncertainty principle

Other equivalent forms of writing the u.p.

t.E

t.E ~

t.E

t.E ~ h

Here the interpretation is different.

Note: If an electron is excited from the ground state to an excited state, after a certain time, the electron
will make a radiative transition (emission of a photon) into another stationary state of lower energy.
The average length of time that the electron spends in an atomic state is called the lifetime of that
energy state
Physical Interpretation
If a stationary state of a system has a lifetime t, then a measurement of energy of the state will be
uncertain by an amount E so that E.t 2 . i.e. when t is finite, the most probable value of
the energy of the state lies between E 12 E and E + 12 E .
OR

The relationship E.t 2 implies that, if a state has a finite lifetime, then its energy can not be
measured exactly ( E 0 ) and, if the lifetime of the state is infinite, then only the energy of the state
can be measured exactly ( E 0).
For the ground state, t

13
i.e. the energy of the ground state is known exactly.
For an excited state,

t is finite

E = is finite.
2t

i.e. the energy of the excited state is not known exactly.

E Natural width of the energy level. (natures limit, and not the uncertainty associated with the
measurement.)
Lifetimes of some levels of atomic hydrogen (in 10 8 s)
Level

2p

3s

3p

3d

4s

4p

4d

4f

Lifetime

0.16

16

0.54

1.56

23

1.24

3.65

7.3

Lifetime of 1s (ground) state = ,

For the 2p level, the natural width, E ~

Lifetime of 2s (metastable) state = 1 7 s

0.16 10

=
4.11 107 eV

Because of the finite energy widths in stationary states, the energy released or absorbed in a transition
is not well-defined. The range of energy of the photon (absorbed or released) is from

( E2 12 E2 E1 ) and ( E2 + 12 E2 E1 )

Energy width of the photon (spectral line) =

E2 = , where 2 is the lifetime of the state with energy E 2 . (The state with energy E 1 is assumed

to have an infinite lifetime.)

Excited state,

E2 + E2

Lifetime, 2 is finite

E2 0

E2

E2 ~

E2 E2
2

is
=
t
2

finite.

Ground state,

E1

E1 = 0

Lifetime, 1 is infinite

E1 ~

= = 0
t
1

When both levels have finite lifetimes (1 and 2 ), energy width of the photon=
the possible ways of decaying of levels into account)

(taking all

14

Illustration of HUP using thought experiments

(i) Diffraction by a slit
Suppose one wants to determine the position x and momentum p x of a particle simultaneously. If the
particle size is in the atomic scale, the act of measurement will appreciably disturb its state of motion.
To determine the x-cdt of the particle moving parallel to the y-axis with known energy, one can
observe whether or not the particle passes through a slit and leave a mark on a screen. The precision
will then be limited by the width of the slit. i.e. x ~ b.
Before the particle went through the slit, its position x was not known but the momentum was known
perfectly.

i.e. p y 0,

px =
0
y
x
Slit
Diffraction
Pattern

Screen

p x

For the matter wave of the particle p =

. Here the disturbance caused by the slit on the matter wave

of the particle results in a corresponding change in the motion of the particle (as seen by the diffraction
pattern produced).
The uncertainty in the particles momentum parallel to the x-axis ( px ) is determined by .
p sin

p sin

px =
2 p sin

From the theory of the diffraction produced by a rectangular slit

b sin=
n=

(n = 1 for the central maximum)

px = 2 p sin = 2

x.px

2h
b

x ~ b

~ h ........... HUP

To determine the position of the particle very accurately (ie to x ), use a narrow slit (ie to b )

15

the central maximum in the pattern is widened

px

Conversely, to reduce the uncertainty in the momentum (ie to px ), use a wide slit (ie to b )

x .

So, the HUP is satisfied in this experiment.

(ii) Heisenberg -ray microscope

To determine the position of an electron placed under a microscope we have to illuminate it with light
of some wavelength .

y
x
Microscope

Objective lens

Photons p =

x
x

Electron

For small ,
Sin tan =

x
y

Pph

For small ,

Pph

Sin tan =

2
y

16
The momentum of scattered photons (by the electron) p ph =

and they must move within the cone

of angle 2 to pass through the objective lens.

p ph sin

p ph sin

The resulting uncertainty in the x-component of the momentum of the photon,

px = 2 p ph sin = 2

2h

sin =

d 2
hd
.
=
y
y

Since some momentum is exchanged between the electron and the photon, the uncertainty in the xhd
component of the momentum of the electron, px = .(1).
y
A microscopes image of a point object is not just a point but a diffraction pattern. The diffraction of
light makes the position of the electron uncertain and this uncertainty is equal to the diameter of the
central maximum in the diffraction pattern.
sin

tan=

x 2
=
y

x
2y

Condition for diffraction, d sin

=
x

2 y sin

= n

For the central maximum,=

d sin

=
,
(n 1)

2 y
..(2)
d
d
hd 2 y
From (1) and (2), for the electron, x.px=

= 2h ~ h (or ~ )
y
d

HUP is satisfied in the detection of the electron.

x =

2y

To improve the accuracy of the measurement of x, we reduce x.

This requires

px .

To improve the accuracy of the measurement of px , we reduce px .

This requires

x .

To see if the time-energy uncertainty principle is satisfied, consider the energy of the electron moving
in the x-direction.
E =

px2
p
E = x px
2m
m

mvx
px
m

= vx px (3)

If t is the time interval required for the position measurement, then the position uncertainty
x = vx t t =

x
.. (4)
vx

17
From (3) and (4), E.t

vx px

x
vx

E.t

x.px

~ h (shown before)

~ h (or )

We see that, at the atomic level, the act of measurement introduces a significant disturbance to the
system (i.e. the electron in experiment (ii)) due to the interaction between the measuring device (i.e.
the microscope with the light source) and the measured quantity (position of the electron).
U.P. implies that we can never define the path of a microscopic particle with absolute precision (i.e.
with zero uncertainty).
However, due to smallness of h, the uncertainties applied by the u.p. ( x.px ~ h ) are much smaller
than the experimental errors in the measured values of x and px for a macroscopic body.
e.g.:- Consider a cricket ball (m ~ 500 g) moving with speed v ~ 150 km/h. The value of v has been
measured with an uncertainty of 0.01 %.
v
100
=
v
p =

0.01
v
100

v
0.01 =

mv p =

0.01 150 103

ms 1 =

100
3600
6.63 1034 J.s
~ h x ~
2.08 103 kg ms 1

mv =

HUP x.px

0.5 kg

2.08 103 kg ms 1

~ 3 1031 m

When measured with the best position measuring device available in the laboratory,
x ~ 0.00001 m

3 1031 m .

Classical mechanics holds true for such large bodies. The word large is used in the sense that the
act of measurement does not disturb the state of motion of the body.
For particles of atomic dimensions (small), paths can not be defined precisely.
Consider the path of a particle in the so called phase space which is used to describe the dynamical
state (x and px values) of the particle.

18

px

The classical path of a (large) particle

in the phase space.

Each point

represents the dynamical state of the

( x, px )

particle and the path is well-defined

(since=
x 0 and =
px 0) .

x
px

The quantum mechanical path of

a (small) particle in the phase
space. Quantum mechanically x
and px have uncertainties as

px

related

by

Therefore, the point representing

the dynamical

x px ~ h

x.px ~ h .
state of the

particle lies in a cell of size

x and px resulting in a path
which is not well-defined.

Example: Melons in quantum land

In quantum land, a strange land, where = 103 J.s, melons with a very hard peel are grown. They
have a diameter of approximately 20 cm and contain seeds with a mass around 0.1 g. Why do we have
to be careful when cutting open melons grown in quantum land ? How big is the recoil velocity of a
melon at the reflection of a visible photon of 628 nm wavelength ? Are such melons visible ?
x ~ 20 cm = 0.2 m,

m = 0.1 g = 104 kg = 0.0001 kg

Applying the H.u.p. x.px ~ for melon seeds, their momentum uncertainty,
103
=
5 103 kg m s 1
0.2
5 103
p

Velocity uncertainty of seeds,

v ~
=
= 50 m s 1
4
m
10
The velocity (mean) with which seeds leave the melon when it is cut open, v ~ v =
180 km h 1
p ~

Momentum of a photon of wavelength 628 nm,

h
2
2
p ph =
103
~ 1 104 kg m s 1
=

628 10

19
Radius of the melon, R ~ 10 cm = 101 m
Mass of the melon, M ~ Volume of melon Density of water ~

4
R3 103 kg m 3 ~ 4 kg
3

Taking the collision between the photon and the melon as elastic, the momentum of the melon after
collision, =
PM

2 pph ~ 2 104 kg m s 1

2 104
The corresponding recoil velocity of the melon = =
5 103 m s 1 =
18, 000 km h 1
4

By the time the photon is seen, the melon is situated elsewhere.

Tutorial 1
1. The position and momentum of a 1 keV electron are simultaneously determined. If its position
is located to within 1 , what is the percentage of uncertainty in its momentum ?
2. An electron microscope uses 40 keV electrons. Find its ultimate resolving power on the
assumption that this is equal to the wavelength of the electrons.
3. Wavelengths can be determined with accuracies of one part in 106. What is the uncertainty in
the position of a 1 X-ray photon when its wavelength is simultaneously measured ?
4.

(a) How much time is needed to measure the kinetic energy of an electron whose speed is 10
m s1 with an uncertainty of no more than 0.1 percent ? How far will the electron have travelled
in this period of time ? (b) Make the same calculations for a 1 g insect whose speed is the
same. What do these sets of figures indicate ?

5. Find the line width and frequency spread for a 1-nanosecond (109 s) pulse from a ruby laser ( =
6.3107 m).
6. Suppose that a beam of electrons with a de Broglie wavelength of 105 m passes through a slit
104 m wide. What angular spread is introduced because of diffraction by the slit ?
7. A probe must always be smaller (at least by a factor of 10) than the object being studied; otherwise
there will be significant perturbation of the position and velocity of the object. Calculate the
minimum particle energy if (a) photons, (b) electrons, (c) neutrons are used to probe a nucleus
whose diameter is 1014 m.
8. The velocity of a proton in the x-direction is measured to be an accuracy of 107 ms1. Determine
the limit of accuracy with which the proton can be located simultaneously (a) along the x-axis (b)
along the y-axis. Repeat for a case in which the particle is an electron.
9. The position of an electron is determined with an uncertainty of 0.1 A. Find the uncertainty of its
momentum. If the electron's energy is of the order of 1 keV, estimate the uncertainty in its energy.

20
Repeat for a proton confined to a nuclear diameter ( 1014 m) with an energy of the order of
2 MeV.
10. Verify that the uncertainty principle can be expressed in the form L. 2 , where L is
the uncertainty in the angular momentum of a body and is the uncertainty in its angular
position. [Hint: Consider a particle moving in a circle.]
11. Using the uncertainty principle arguments, show that electrons can not be present within nuclei.
You may take the nuclear diameter to be 1014 m.
12. Use the uncertainty principle to determine the radius of the first Bohr orbit of the hydrogen atom.
13. An atom can radiate at any time after it is excited. It is found that in a typical case the average
excited atom has a lifetime of about 108 s. That is, during this period it emits a photon and is deexcited. (a) What is the minimum uncertainty in the frequency of the photon ? (b) Most
photons from sodium atoms are in two spectral lines at about = 5890 . What is the fractional
width of either line / ? (c) Calculate the uncertainty E in the energy of the excited state of the
atom. (d) From the previous results determine, to within an accuracy E, the energy of the excited
state of a sodium atom, relative to its lowest energy state, that emits a photon whose wavelength is
centered at 5890 .
14. Use the uncertainty principle involving position and momentum to estimate the minimum energy
of a linear harmonic oscillator.
15. Consider a microscopic particle moving freely along the x-axis. Assume that at the instant t = 0
the position of the particle is uncertain by the amount x0 . Calculate the uncertainty in the
measured position of the particle at some later time t.
16. A boy on a top of a ladder of height H is dropping marbles of mass m to the floor and trying to hit
a crack in the floor. To aim, he is using equipment of the highest possible precision. (a) Show that
12

the marbles will miss the crack by an average distance of the order of ( m )

( H g )1 4 , where g

is the acceleration due to gravity. (b) Using reasonable values of H and m, evaluate this distance
(c) If the marbles are perfectly elastic and if they rebound again to the height H from the floor,
what is the expectation of the minimum horizontal distance of displacement from the point from
which it was dropped ?
17. The beam from a laser is usually extremely well-collimated. By applying the uncertainty principle
to estimate the transverse momentum of the photons, show that a helium-neon laser beam which
initially has diameter 1 mm can be collimated to an angle of about 3 103 degrees. How small
would be the filament of an ordinary household torch have to be to achieve the same collimation?

21

Wave function

We can talk about the path of a large object in the sense of classical mechanics. For such an object it is
possible to solve the classical equation of motion (Lagranges equation) and obtain an expression for

r (t ) and hence describe the motion by defining a well-defined path.

But, we cannot talk about the trajectory of an atomic particle and, to describe its motion, we may use
the associated de Broglies matter field. In a de Broglie wave, the matter field is assumed to vary in
space and time (similar to e/m field varies in space and time in a light wave or pressure field varies
in space and time in a sound wave).and this variable quantity characterising de Broglie waves is
called the wave function. The value of the wave function associated with a moving particle at the
point x, y, z in space at the time t is related to the likelihood of finding the particle there at that time.
Wave function contains the maximum information that we have about the particle in a given

dynamical state. All observable properties of the particle can be obtained by (r , t ) . In quantum

mechanics, to obtain (r , t ) we solve the Schrodinger equation.

Eg: The electric field of a sinusoidal e/m wave of w.l. and freq

can be written as

=
E ( x, t ) A sin 2 ( x t ) . The wave function of a particle moving in the x-direction with
a precise value of energy (i.e.) and linear momentum (i.e.) can be written as

=
( x, t ) A sin 2 ( x t ) . The quantity E is a (radiation) wave associated with a photon
and is a (matter) wave associated with a material particle.
Suppose we have a particle which is confined to a small region of space (eg:- an electron confined to
an atom, diameter ~ 1010 m). Its associated matter wave may be expressed in terms of standing waves
(the value of the wave is fixed in at each point of space) localized in the given region, with the
instantaneous value varying from point to point within the region and practically zero outside the
region. Let ( x) be the wave function associated with the particle.

22

( x)

( x)

Amplitude

Intensity

x
Particle is most
likely to be found

( x) = * ( x). ( x) is the intensity of the matter field or the position probability density.
Position probability density gives the probability per unit length of finding particle at a given point.

When the motion of the particle is in 3-d space, its wave function (r ) = ( x, y, z ). Wave

function can have a time dependence, (r . t ) or ( x, y, z , t ) .

21

Wave function

We can talk about the path of a large object in the sense of classical mechanics. For such an object it is
possible to solve the classical equation of motion (Lagranges equation) and obtain an expression for

r (t ) and hence describe the motion by defining a well-defined path.

But, we cannot talk about the trajectory of an atomic particle and, to describe its motion, we may use
the associated de Broglies matter field. In a de Broglie wave, the matter field is assumed to vary in
space and time (similar to e/m field varies in space and time in a light wave or pressure field varies
in space and time in a sound wave) and this variable quantity characterising de Broglie waves is
called the wave function. Wave function is a mathematical tool used in quantum mechanics to
describe any physical system and it is a function from a space that maps the possible states of the
system into the complex numbers. The value of the wave function associated with a moving
particle at the point x, y, z in space at the time t is related to the likelihood (probability) of finding
the particle there at that time. Wave function contains the maximum information that we have about
the particle in a given dynamical state. All observable properties of the particle can be obtained by

(r , t ) and in quantum mechanics, it is found by solving the Schrodinger equation.

Eg: The electric field of a sinusoidal e/m wave of w.l. and freq

can be written as

=
E ( x, t ) A sin 2 ( x t ) . The wave function of a particle moving in the x-direction with
a precise value of energy (i.e.) and linear momentum (i.e.) can be written as

=
( x, t ) A sin 2 ( x t ) . The quantity E is a (radiation) wave associated with a photon
and is a (matter) wave associated with a material particle.
Suppose we have a particle which is confined to a small region of space (eg:- an electron confined to
an atom, diameter ~ 1010 m). Its associated matter wave may be expressed in terms of standing waves
(the amplitude of the wave is fixed in at each point of space) localized in the given region, with the
amplitude varying from point to point within the region and practically zero outside the region. Let

( x) be the wave function associated with the particle.

( x)

( x)

Intensity

x
Particle is most likely to
be found

22
2

( x) = * ( x). ( x) is the intensity of the matter field or the position probability density.
Position probability density gives the probability per unit length of finding particle at a given point.

When the motion of the particle is in 3-d space, its wave function (r ) = ( x, y, z ). Wave

function can have a time dependence, (r . t ) or ( x, y, z , t ) .

Wave function contains the maximum information that we have about the particle (system) in a
given dynamical state as allowed by the uncertainty principle. All observable (i.e. measurable)

properties of the particle can be obtained by (r , t ) .

In classical mechanics, once we obtain r (t ) (by solving Lagrangian equation) we have solved the
problem.

In quantum mechanics, once we obtain (r , t ) (by solving Schrodinger equation) we have solved
the problem.

In classical mechanics, position of a particle is given by r = r (t ) . Then we can find
Velocity

dr

v =
dt

Acceleration

d2 r

a =
dt 2

Angular momentum

d2 r
F = m
dt 2

dr

p = m
dt

L= r p

Total Energy

E = k.e + p.e =

Force
Linear momentum

2
1 dr

m + V (r , t )
2 dt

In quantum mechanics, to get all the above information, what we have is the wave function.

Properties of the wave function

Consider a particle moving in 3-d

(1) (r , t ) is in general a complex function of r = ( x, y, z ) and of time t and is sometimes called

the probability amplitude. (r , t ) is an abstract quantity which is interpreted statistically.

(r , t ) and c(r , t ) , where c is a complex no, represent the same state of the particle.

(2) The probability of finding the particle in a state described by the wave function (r , t ) within

the volume dV = dx .dy .dz about the point r = ( x, y, z ) at time t =

dV dr d 3 r = dx .dy .dz (in cartesian co-ordinates)

2
(r , t ) dV ,

23

2
If P(r , t ) dr = (r , t ) dr

P(r , t ) =(r , t ) =* (r , t ).(r , t )

dy

dz
dx

P(r , t ) is called the position probability density.

y
x

e.g.

i( k x + k y + k z t )

i( k r t )
y
z
=
(r , t )
Ae = Ae x

* (r , t ) = A*ei( k r t )

*
=
r , t)
A A*
A 2 , if A is complex.
P(=
=
= A2 , if A is real.

(3)

Probability of finding the particle within the volume V =

(r , t )

dr

(in 3-d)

Prob. of finding the particle within the points a and b on the x -axis =

( x, t )

dx

(in 1-d)
(4)

--

Probability interpretation of the wave function

The wave function (r , t ) is said to be square-integrable, if the normalization integral

2
(r , t ) dr is finite.

all
space

Note: In this course, we work with square-integrable wave functions only.

If

2
(r , t ) = f ( x) f ( y ) f ( z ) f (t )

2
=
(r , t ) dr
all
space

(5)

=
f ( x) f ( y) f ( z ) f (t ) dx dy dz

all
space

f ( x) dx

f ( y ) dy

f ( z ) dz. f (t )

Since the probability of finding the particle somewhere must be unity, (r , t ) must be

normalized to unity

all
space

2
(r , t ) dr = 1 , for all t values.

24
Since and c represent the same state of a particle, it is convenient to work with square
integrable wave functions with the value of c chosen so that the wave function is normalized
to unity.

2
(r , t ) dr = finite (say a )

all
space

1
a

all
space

1
2

(r , t ) dr =
1
1

a (r , t ) dr =
all
space

2
=
(r , t ) dr

1,
where
(r , t )
=

all
space

(r , t )

(r , t ) is a wave function normalized to unity. and represent the same state of the

system and it is more convenient to work with .

Eg:
(i) Normalize the wave function ( x, t ) = ei( k x t ) which represents a plane wave.
By writing ( x, t ) = A ei( k x t ) , where A is the normalization constant,
* ( x, t ) = A* ei( k x t )
2

Setting

( x, t ) =
dx

all
space

x
d=

A =

A can not be evaluated

plane wave functions can not be normalized.

2
(ii) Normalize the wave function ( x, t ) = e a x i bt
2
Writing ( x, t ) = A e a x i bt

Setting

( x, t ) dx=

all
space

2 A

* ( x, t ) = A* e a x

1
=1
2 2a

14

2a
A =

2 a x 2

dx=

+ i bt

A 2

e 2 a x dx

14

2a
( x, t ) =

2
e a x i bt

We can generalize the above results for the case of a system of n particles. Eg: A manyelectron atom.

25

Wave function of particles, (r1 , r2 , r3 , ........., rn , t ) , where r1 , r2 , r3 , ........ , rn are the

position vectors of particles.
Normalization integral =

(r1 , r2 , r3 , ........, .rn , t )

dr1dr2 .dr3 ...........drn

(6) The wave functions 1 (r ) and 2 (r ) are said to be orthogonal if their scalar product,

1* (r ) 2 (r ) dr = 0

or

equivalently

all
space

2* (r ) 1 (r ) dr = 0 .

all
space

Dirac Bracket Notation

The scalar product of two functions

1* (r ) 2 (r ) dr is denoted by 1 2

Bracket.

all
space

1 2
In Dirac notation,

(r )

i. If = c 1 + d 2

all
space

* (r )

a ket vector

Note: * (r ) (r ) and only

1* (r ) 2 (r ) dr

(r ) (r ) dr =

= c 1 + d 2

ii. If * = c* 1* + d * 2*

= c* 1 + d * 2

iii. If c is a complex no

1 c 2 = c 1 2
c 1 2

= c* 1 2

iv. If the two wave functions 1 and 2 are orthogonal,

1 2 = 0

In Dirac notation,

a bra vector

all
space

2 1 = 0 .

or

v. For the scalar product of two wave functions 1 (r ) and 2 (r )

*

1 2 = 2 1 .

vi. A wave function (r ) is normalized, if

* (r ) (r ) dr = 1 .

all
space

1* (r ) 2 (r ) dr = 0

we have

26

In Diracs notation,

= 1.

vii. If 1 (r ) , 2 (r ) and 3 (r ) are wave functions 3 1 + 2=

3 1 + 3 2

Superposition Principle

If 1 (r , t ), 2 (r , t ), 3 (r , t ), ................ , N (r , t ) are wave functions which represent different

states of a system (eg:- the ground and excited states of the electron in a hydrogen atom), then
Mixture
of states

where
2

(r , t ) = c11 (r , t ) + c2 2 (r , t ) + .......... + cN N (r , t ) =
c1 , c2 , c3 , ........., cN

are

c1 + c2

+ c3

+ ......... + cN=

constants
N

n =1

cn=

(mixing

cn n (r , t )

n =1

(N can be finite or infinite)

coefficients)
such
that

1 , is also a wave function describing a

possible state of the system. In Dirac notation, =

cn

n =1

cn n

is interpreted as the probability of the system in state (r , t ) being found in the state

n (r , t ) on measurement.
Eg:

Hydrogen atom
Stationary State

Wave function

Nth excited state

N (r , t )

Probability of finding
the electron on
measurement

cN

c4

c3

c2

c1

.
.
.
3rd excited state

2nd excited state

1st excited state
Ground state

4 (r , t )

3 (r , t )

2 (r , t )

1 (r , t )

When we have a set of wave functions 1 , 2 , 3 , ............. , N , we want each of them to be

normalized (to unity) and every pair to be orthogonal ----- An Orthonormal set (basis).

*
*
*
i.e. 1* 1 d=
r
r
r
...............
=
r
2 2 d=
2 2 d=
N N d=
all
space

all
space

all
space

all
space

27
and

all
space

1* 2 d=
r

all
space

*2 3 d=
r

all
space

1* 3 d=
r

Consider the Kronecker Delta function, defined as

all
space

*3 4 d=
r

mn = 1,

0,

=
.................

if m = n
if m n

Then, the condition of orthonormality of a set of wave functions is

all
space

*m n dr = mn

( m = n gives the condition of normalization and m n gives the condition of orthogonality.)

m n =
mn .

In Diracs notation, the condition of orthonormality is

Consider,

(r , t) =

c11 (r , t) + c2 2 (r , t) + .......... + cn n (r , t) + ................ + cN N (r , t)

Multiplying throughout by *n and integrating over all space,

all
space

*n=
dr

c1

all
space

*n 1dr +

............ + cn

all
space

*n n dr + ......... + cN

=0
cn

all
space
N

n =1

*n (r , t ) (r , t )dr =

cn n

* dr
=

all
space

*
=
dr

all
space

=1
n

all
space

*n N dr
=0

c1 , c2 , c3 , ............, cN can be determined.

cn* *n

*
=

n =1

m 1
all =
space
N

* *
cm
m

=
m 1=
n 1

cn n dr
=

=
n 1

*
cm
=
cn mn

Normalization of ( r , t) requires that

cm* cn

=
m 1=
n 1

=
cn* cn

=
n 1

=
n 1

* dr =1 .

cn

all
space

*m n dr

This requires

all
space

n =1

cn

= 1.

Observables and Operators

Operator

+ Wave function

Observable (l.m., a.m, k.e, p.e, posn, tot.energy, etc)

28
e.g.:

To get the length of the table we measure it with a ruler.

In q.m., with each observable, there is an associated operator.

i. Position co-ordinate

x,

Operator is

x = x

Position vector

r,

Operator is

r = r

ii. A component of linear momentum p x , Operator is

Linear momentum vector p ,

In p = i ,

= i
i x
x

p = = i
i

Operator is

p = ( p x , p y , p z )

p x =

and

(in 1-d)
(In 3-d)

= ,
,
.
x y z

Position and linear momentum operators have very simple forms. More complicated operators are
built up from their classical analogue.
If an observable F can be written in classical mechanics, as a function f ( A1 , A2 , A3 , ........., An ) of
other observables A1 , A2 , A3 , .........., An then, the operator F which represents the observable F
can be written in quantum mechanics, as f ( A1 , A 2 , A3 , ........, A n ) , where A1 , A 2 , A3 , .........., A n are
the operators representing the observables A1 , A2 , A3 , ........, An .
iii. Kinetic energy operator

T
=

Note:

=
T

px2
2m

in classical mechanics

p x2
=
2m

p x2

2 2
2m x 2

=p x p x

2 2

2m

(in 1-d)

in quantum mechanics
= i

2

2

x x
x 2

(in 3-d)

iv. Orbital angular momentum operator

in classical mechanics
L= r p

L=

Note:

r p =

r i

in quantum mechanics

(in 1-d)

29


In classical machines r p = p r

( since

In quantum machines r p p r

i.e. the order of operation is important in quantum mechanics.

v. Total energy operator

E= T + V (r , t )
E=

T + V (r , t )

p 2

+ V (r , t=
)
2m

r ( i) ( i) r

in classical machines
in quantum machines

2 2

+ V (r , t )
2m

H Hamiltonian

Properties of Operators
1. Operators act on states (wave functions) to produce new states (new wave functions).
Let A be an arbitrary operator

A 1

= 2 (if 1 is normalized but 2 is not

normalized, we can normalize it so that, c 2 = 3 )

In Diracs notation, A 1
Note:

2 .

Unless otherwise stated, operators act on everything to the right of them.

1 A 2
e.g:
=
1

1 A 2
=

= 1 A 2

)
ei k 2 x ,
A
=

ei k1 x ,
=
2

i k2 x
ei k1 x
e
=
x

i k2 eik1 x ei k2 x
=

ik2 ei( k1 + k2 ) x

2. Two operators A and B are said to be equal, if for any wave function , A = B .
3. Operators can be added, subtracted or multiplied to one another to get new operators.
If B and C are operators, =
A

B C and A = B C are operators.

A=

i.e. for any wave function , we have

( B C )
( B C )

4. Operator A is linear if it has the property

A ( c1 1 + c2 2 )

A ( c1 1 ) + A ( c2 2 )
= c1 A 1 + c2 A 2

30
where c1 and c2 are complex numbers.
We consider linear operators only in this course. The reason is that linear operators are

associated with physical observables (e.g: x, p, L, T , V , E )
If A and B are linear operators, the sum A + B and the difference A B and the product

A B are linear operators.

For any ,

( A

= A B

( )

=
A B

( )

=
A B

A B

Any three operators A , B and C satisfy the associative property.

=
A B C

For any ,

=
A B C

=
A ( B C )
( )
( A B ) C
=
A ( B C )
( A B ) C
=
A B C

Any three operators A , B and C satisfy the distributive property.

+ B C
( A + B ) C = AC
+ B C
( A + B ) C = AC

A ( B + C ) =
A B + AC

A ( B + C ) =
A B + AC

For any

Similarly

The square of an operator A is defined as A 2

( )

=
A 2

A A

( )

A A
=

A A

In general, the order of multiplication of operators is important. i.e. A and B are not necessarily
commute

i.e.

A B B A , in general

5. Hermitian operators
Suppose A is an operator and represent two states. Then, if

all
space

* (r , t) A (r ,=
t ) dr

( A (r , t ) )

( r , t ) dr

- Condition of Hermiticity

all
space

is called a Hermitian operator.

is true for all and , A

In Diracs notation,

31
*

All the physical observables are represented by Hermitian operators.

is an operator representing an observable A and is a wave function of a system and,

6. If A

a , where a is in general a complex number, then the system is said to be an

eigenstate of the operator A with an eigenvalue a. is called an eigenfunction.

= a
A

Physical significance:

Eigenvalue equation

( In Dirac notation,

= a

The eigenvalue equation represents a precise measurement of an

observable A which yields the value a.

Properties of eigenfunctions:
(i)

An operator can have more than one eigenfunction.

(ii)

Different eigenfunctions of the same operator can have the same eigenvalue or different
eigenvalues.
eg: Consider the operator p x = i
x ( x)
p

and the wave function ( x)

x

ei k x .

ik x
=
i
e
=
k ei k x =
k ( x )
x

( x) is an eigenfunction of p x with eigenvalue k .

Consider

( x, y , z )

the

operator

x = i
p

and

the

wave

function

ei k x f ( y , z ) .

ik x
x ( x, y, z ) =
p
e
f ( y, z ) =
i
k e i k x f ( y , z ) =
k ( x , y , z )
x

( x) and ( x, y, z ) are eigenfunctions of p x with the same eigenvalue k .

Consider the operator p x = i

2 ( x ) = ei k

x 1 ( x )

=
p

and the wave functions 1 ( x) = ei k1 x and

x

x 2 ( x )
=
k1 1 ( x ) and
p

k 2 2 ( x )

1 ( x) and 2 ( x) are eigenfunctions of p x with different eigenvalues

k1 and k2 .

The whole set of eigenvalues of an operator is called its spectrum and a spectrum may contain a
discrete or continuous set of values.

32
7. The eigenvalues of a Hermitian operator are real.
Pf: Let A be a Hermitian operator. Then, by definition of a Hermitain operator, for and

all
space

( A )

* A =
dr

dr

all
space

all
space

( A )

dr .. (1)

a . (2)

* A =
dr

When = ,

all
space

The eigenvalue equation

=
A

Taking the complex conjugate

( A )

= a * * . (3)

By substituting in equn (1) from equns (2) and (3),

*
* *
dr
a =
a dr
all
space

Note: A

all
space

* *
A

( a a* )

* dr 0

( a )*

and

= a * * .

* dr = 0

all
space

a a* =
0

a = a*

a is real.

all
space

Note: The inverse of the above statement is not necessarily true.

8. The eigenfunctions of a Hermitian operator corresponding to different eigenvalues are
orthogonal.
=
A
n

Pf: It is given that,

an n

It is required to prove that, if am an

( A n )

all
space

m dr =

*
( an n ) m dr

all
space

n* A m dr

n* am m dr

all
space

all
space

and

A
m =

all
space

am m

m* n dr =
0.

Condition of Hermiticity

33
an*

all
space

*n =
m dr

an is real

an am

am

all
space

n* m dr

an* = an

all
space

( an

am )

n* m dr =0

all
space

n* m dr =0

n is orthogonal to m .

(Note: When an = am , we can not decide whether n is orthogonal to m or not.)

9. If two or more eigenfunctions have the same eigenvalue with an operator, then any linear
combination of these eigenfunctions will have the same eigenvalue.
Pf: Let A be the operator and, n and m be the eigenfunctions corresponding to the
eigenvalue a.
A m = a m ,

A n = a n

(given)

Linear combination, = c m m c n n , where c m and cn are complex numbers.

A =

A ( cm m cn n )=

cm A m cn A n
= cm .a m cn .a n

= a ( cm m cn n ) = a

is an eigenfunction of A with the eigenvalue a.

Degeneracy: An eigenvalue a is said to be degenerate if there is more than one linearly

independent eigenfunctions belonging to that eigenvalue.
The number of such eigenfunctions is the called the degree of degeneracy.
eg: Consider A with 1 , 2 , 3 , 4 , ..............., n are all different eigenfunctions.
If A 1 = a 1 , A 2 = a 2 , A 3 = a 3 , ................, A n = a n , then
a degeneracy exists and the degree of degeneracy = n
The eigenvalue a is said to be n-fold degenerate.
10. When two (normalized) eigenfunctions of a H. O. corresponding the same eigenvalue are not
known to be orthogonal, it is still possible to find two eigenfunctions of the operator having the
same eigenvalue and satisfy the normalization and orthogonality conditions.
Let A be a Hermitian operator and 1 and 2 be two normalized eigenfunctions,
corresponding the same eigenvalue a and not known to be orthogonal.

34
In Diracs notation,
A 1 = a 1
1 and 2 are normalized

A 2
1,

=
1 1

= a 2
=
2 2

Construct two linear combinations of 1 and 2 as

1 =

c1 1 + c2 2 ,

2 =

c3 1 + c4 2 ,

where c1 , c2 , c3 and c4 (assume as real) are 4 unknown constants to be evaluated.

Since it is difficult to evaluate all 4 constants, choose c1 = 1 and c2 = 0 .

1 = 1 , and it is therefore already normalized.

c3 and c4 should be evaluated such that, 2 is normalized and orthogonal to 1 .

i.e. we require

1 2

=0

2 =
2

=1

0.

1 =
2

1 ( c3 1 + c4 2

=0

c3 1 1 + c4 1 2

2 2

1,

( c3 1

+ c4 2

c32 1 1 + c3c4 1 2

c32 + c42 + c3 c4 ( 1 2

) ( c3 1

=0

c3 = c4 1 2

+ c4 2

1
=

+ c3c4 2 1 + c42 2 2

+ 2 1

=1

)2

=1

Substituting for c3 ,

c42 ( 1 2
=
c4

When 1 2

0,

)2

+ c42 c42
1 2

((

1 = 1

and

1 2

) =1

c3 = 1 2

1 +
= 1 2
1 1 2

1 2

2
2

are

normalized and orthogonal to each other. In addition, according to result 9, they have the same
eigenvalue a as do 1 and 2 .
The above procedure is known as the Schmidt orthogonalization procedure and it can be
extended to any number of eigenfunctions.
In result 8, we proved that the eigenfunctions of H. O. corresponding to different eigenvalues as
orthogonal. So, if we consider results 8, 9 and 10 together, we can conclude that the set of
eigenfunctions of a H. O. can be made to satisfy the normalization and orthogonality conditions.

35

11. If A and B are two operators and (r , t ) is some wave function,

(r, t ) =BA
(r, t ) ?
Question: Is AB
Answer:

Not in general.

B p x =
i
x

Eg: A x =x,
Consider the state ( x)
( x) =
AB

x ( x) =
xp

( x) =
BA

p x x ( x) =

x ( p x ( x) ) =

i x

( x)
x

( x ( x ) )
x

= ix ( x ) i ( x)
x

p x ( x ( x) ) =

x ( x) p x x ( x)
xp

x
( xp

x p x x =
xp
i

and

x p x ( x) p x x ( x) =
i ( x )

p x x ) ( x) =
i ( x) for any ( x)

Define the Commutator A , B of two operators A and B as A ,=

B
A , B =

A B B A .

B , A

Note: Commutator A , B is also an operator.

A , B = 0
If A , B (r ) = 0 , for any (r )

A B =B A

the

two

operators A and B are said to commute.

x p x x =
xp
i

Now consider,

[ x,

p x ] = i

x and p x are called canonically conjugate observables.

Since y , p y = i , [ z, p z ] = i , the pairs y, p y and z , pz are also canonically conjugate
observables [=
x , p x ]

y , p y

z, p z ]
[=

i (A)

For all other pairs of x , y and z and p x , p y and p z we get zero commutators.

x , y ]
y , z ]
z, x ]
[=
[=
[=
=

p x , p y
=

x , p y

p y , p z

0
p z , p x ]
[=

y , p x ]
x , p z ]
y , p z ]
z, p x ]
[=
[=
[=
[=

z, p y

0 (B)

36
Relationships (A) and (B) can be combined to be given in the form
xi , p j = i ij

i, j=

1 x,

i, =
j

2 y,

i, =
j

3 z

12. Every operator commutes with itself or any function of itself

( )

A , A
=

=
0, A , f A

( )

0 , where f A = A 2 , e A , ........

Commutator algebra
(i) A , B =

B , A

(ii) A , B C=

A , BC
(iii)=

A , B A , C

A , B C + B A , C

0
(iv) A , B , C + B , C , A + C , A , B =

) ( B C ) A
AC
( BA
) =
CA
= AB

Proof: (ii) A , B C =

A B C

BA

AB

CA
)
( AC

= A , B A , C
Prove (i), (iii) and (iv) as exercises.
13. If two operators commute, then we can always find a set of eigenfunctions which are
simultaneous eigenfunctions of each operator.
Proof: It is given that, A , B = 0 and for the set of functions { n } , n = 1, 2, 3.........

A n = a n . (1)
A , B =0

n = 1, 2, 3.........

=BA

AB

Operate with B on equation (1).

( )
A ( B n )

B A n

= B ( a n )

) = B ( a )
( BA
n
n

A = a

= a B n

) = aB
( AB
n
n

where = B n .

Two cases are to be considered

(i) a is non-degenerate.(easy to prove)
We consider case (i) only in this course.

(ii) a is degenerate (difficult to prove)

37

A n = a n . (1)

A = a .. (2)

Since a is non-degenerate, n and should not be linearly independent.

i.e.

= b n

B n = b n ,

(should be)
n = 1, 2, 3

Therefore { n } , n = 1, 2, 3, .......... are simultaneous eigenfunctions of both A and B .

Case (ii) can also be proven with some difficulty. Therefore, the result given under (13) can be
considered as always true.
i.e. when A , B = 0 , the pair of observables represented by the operators A and B can be
measured simultaneously with perfect accuracy ( A =B =0 ) .
However, if A , B 0 , then the U.P applies to the observables represented by these
operators ( A B )
The observables which can be measured simultaneously with perfect accuracy are called
compatible observables.

Eg: Components of r , i.e. x, y, z

x , y ]
y , z ]
z, x ]
[=
[=
( since [=

p x , p y
Components of p , i.e. p x , p y , p z since =

p y , p z

0)

p z , p x ]
[=

Incompatible observables

x and p x

since [ x , p =
x]

i x px / 2

y and p y

since y , p y =

i y p y / 2

z and p z

since [ z, p z=
]

i z pz / 2

14. Expectation (mean, average) Values

If a series of measurements of an observable A (represented by A ) is made on a group

(ensemble) of systems in a state described by the wave function. (r , t ) , then the expectation
value of A can be given by

Aavg

* (r , t ) A (r , t ) dr

all
space

all
space

* (r , t ) (r , t ) dr

38

If (r , t ) is normalized, Aavg

In Diracs notation, A

all
space

* (r , t ) A (r , t ) dr

and, if is normalized,

If A is representing a physical observable

( A )

* A =
dr

all
space

dr

A is Hermitian.

Condition of Hermiticity

all
space

Consider Aavg
Aavg=

A dr (1)

dr .. (2)

( A )

Using the condition of Hermiticity.

*
Aavg

Taking complex conjugate of (1)

(assuming as normalized)

( A )

( A )

dr

dr=

Aavg (using (2))

Aavg is a real value.

In Quantum mechanics, the uncertainty associated with measurements of an observable A is

defined (Statistically) as
=
A
=
A

A2 2 A A +

(A

12

=
A A2

12

A2

2 A A +

2 1 2

2 1 2

When is normalized,
A

all
space

* A dr ,

A2

A A

* A A dr

all
space

15.The adoint of an operator

In many situations, it is convenient to work with non-Hermitian operators. Then it is useful to introduce,
the adjoint or Hermitian conjugate of an operator A which is denoted by A ( - dagger)

A satisfies the relation,

39

( A (r, t ) )

* (r, t ) A (r, t ) dr =

all
space

(r, t ) dr

all
space

for any functions (r , t ) and (r , t )

If A is not a H. O.

If A is a H. O.

For any operator, if A = A , then A is said to be self-adjoint. A self-adjoint operator is

Hermitian.
In general A A *

Eg: Consider A =
p x =
i
x

Since p x is a H.O.,

p x =

i
p *x =
x

p x =

p x p *x

Also, in the matrix representation of operators;

If=
A

=
A
But

( )

=
AT

a*

c*

=
A
*

b*

d *
a*

b*

c
a
=

d
b

c*
A* ( unless b* = c* )
*
d

Eg: By using the definition of a Hermitain conjugate, show that

i.

( A

ii.

( A B )

( )

iii. cB
iv.

( A )

=A B

= B A
= c* B , where c is some complex number.

= A

For any operator A , if Q = e i A , then Q =

(i A ) n
n ! , where A n in the expansion means
n

the operator A applied n times.

16. If = A , where A is some operator, and is the bra of the ket , then = A .
Pf:

For any and , we have

40

A =

*
A =

A =

17. Unit, Inverse, Unitary and Projection Operators

The operator that leaves unchanged is called a unit operator.
i.e. I =

I =

In Diracs notation,

eg: = I

If for any operator A , there is B such that =

BA

=
AB

I , then B is said to be the inverse of

A and denoted by A 1 .

U
An operator U , such that U
=

U
U
=

I is called a unitary operator.

is said to be idempotent if
is Hermitian, it is called a
2 =
. If, in addition,
An operator

projection operator.
Any function can be expressed in terms of two orthogonal functions and by means of
a projection operator.
and =
Hint: writing = + with =

(1 ) , show that

=0 .

18. Closure Relation *

Consider the discrete orthonormal basis set

{ n }.

If it is a complete set, every wave

can be expanded uniquely on the n s as

= cn n .

function

As shown before, cn are given by cn = n .

=

=
cn n
n

=
n n
n

Since the above result is true for any

Conversely,=

=
I

=
n n
n

n n=

n n

cn n
n

n n
n

= I - Closure Relation
with=
cn

n .

Note: The above results can be also shown to be true when the orthonormal set is a continuous
one. When

{ m } is a continuous orthonormal set, the closure relation takes the form

m d m = I .

Consider the discrete orthonormal basis set { n (r )} . If it is a complete set, every wave

function (r ) can be expanded uniquely on the n (r ) s as

41

=
(r )

=
cn n (r )
n

n* (r ) (r )d r n (r ) .
n

Interchanging the summation and the integration,

*

d
r

(
r
)

(
r
)

(
r
)

n
n

(r ) =
From this it can be deduced that

(r ) =
d r (r ) (r r ), where

function

(r =
r)

1,

0,

n* (r ) n (r )

=
(r r ) and the Diracs Delta

=
if r r

if r r

Note: The closure relation expresses the completeness of the set of functions

{ n }.

Not all

Hermitian operators possess a complete set of eigenfunctions and those that do are called
observables.

Tutorial 2

Operators, Eigenvalues and Eigenfunctions

1. If A and B are two Hermitian operators, show that (a) A B is hermitian, (b) AB and BA may not
be hermtian (under what condition are they hermitian ?), but that (AB + BA) and i(AB BA) are
both hermitian, (c) (AB BA) is not hermitian (d) the expectation value of A2 is always real and
non-negative, (e) if A2 = 2, find the eigenvalue.
2. If A and B are two operators with adjoints A and B respectively, show that (a) (AB) = B A, (b)
(A B) = A B, (c) A = A , where A = (A), (d) (cA) = c*A, where c is a complex number
(e) (A + A) and i(A A) are hermitian for any operator, as is AA. Thus show that A can be put
as a linear combination of hermitian operators (f) If A is not hermitian, is AA hermitian ?
3. Given that the inverses A1 and B1 are known. (a) What is the inverse of S = AB ? (b) Does you
answer to part (a) depend on the hermiticity of A or B ? (c) Employ your answer to part (a) to
establish that if A1A = I, then AA1 = I.
4. The operator Q satisfies the two equations QQ = 0, QQ + QQ = 1. The Hamiltonian for a
system is given by H = QQ, where is a real constant. (a) Show that H is Hermitian. (b) Find
an expression for H2, the square of H, in terms of H. (c) Find the eigenvalues of H as allowed by
the result of part (b).
5.

d ( x)
For the two operators: P ( x) = x3 ( x) and Q ( x) = x
, find the commutator P , Q .
dx

6. Suppose the two operators, P and Q, satisfy the equations: P = QQ + 3, P = QQ + 1.

(a) Show that P is self-adjoint (b) Find the commutator [Q, Q]. (c) Suppose is an eigenfunction
of P with eigenvalue p: P = p. Show that if Q 0, then Q is an eigenfunction of P and
find the eigenvalue.

42
dB dA
d
B . Is the following result
+
( AB) = A
dt
dt
dt
dA2
dA
dA 1
dA1
always true for an operator A:
. ? Show that
= A1
A .
= 2A
dt
dt
dt
dt

8. If A =
+ x and B =
x , find the products AB and BA and hence show that [A, B] = 2.
x
x

9. Show that the operator relation ei xa p ei xa =

p + a holds.

7. For any two operators A and B, it is given that

10. Write out fully the operators corresponding to the three rectangular components of the orbital

angular momentum L = r p .
11. Show that the linear momentum operator id/dx is hermitian.
12. Indicate which of the following functions are eigenfunctions of the operator d/dx: (a) eikx, (b) ex,
(c) sin kx. Indicate in each case the eigenvalue. Repeat for the operator d2/dx2.
13. Show that the free-particle wave functions (x) = eikx are eigenfunctions of the momentum
operator corresponding to the eigenvalues k, respectively.
14. Suppose one wants to find the eigenvalues of a Hermitian operator A. Show that if there exist
another operator X such that [A, X] = kX, then k is the spacing between the eigenvalues of A.

43

The Time-Dependent Schrodinger Equation (TDSE)

This basic equation of non-relativistic quantum mechanics was proposed by E. Schrodinger in 1926
and is also called the wave equation.
In 3-d,

(r , t )
i
=
t

H (r , t ) , where H

In 1-d,

( x, t )
=
t

H ( x, t ) , where H

2 d 2
=

+ V ( x, t )
2m dx 2

2 2

+ V (r , t )
2m

This equation gives the time evolution of the wave function of a of a particle (quantum system) of

mass m moving in a region of potential energy V (r , t ) . As solutions to the above equation one can
obtain the wave function of the system.

In Diracs notation, the TDSE is given in the form, i

=
H =
H
t

Properties of the TDSE

It is a linear equation ( appears only in power in one).

It is a 2nd order differential equation in r and t.

If 1 (r , t ) and 2 (r , t ) are solutions of the TDSE, then = 1 + 2 is also a

solution of the TDSE. This is a direct result of the linearity of the TDSE.

Probability Current Density

(r , t ) =
* (r , t ) (r , t )
Position probability Density, P(r , t ) =

all
space

P(r , t )d r = 1

(true for all t values)

P (r , t )d r = 0 .

t all
space

To show that the above relationship is satisfied in Schrodinger theory,

P(r , t ) =
* (r , t ) (r , t )

P(r , t ) =
* (r , t ) (r , t ) + * (r , t ) (r , t ) (1)
t
t
t

2

(r , t )

Consider TDSE
=
2 + V (r , t ) (r , t ) . (2)
i
t
2m

2 2
* (r , t )

TDSE*
i
=
+ V * (r , t ) * (r , t ) . (3)
t
2m

V (r , t ) = V * (r , t ) if V is real , and we do not consider complex potential energies in this course.

*
Now by substituting for
and
from equations (2) and (3) in (1),
t
t

1 2
P
2
2
* ( ) (*)
=
(

*)

* ( 2 ) =

i 2 m
2m
t
2m i

Consider

44
Define the Probability Current Density or Probability Flux Density as

j (=
r , t)

Note:

* ( ) (*)

2mi

j 0 only if is complex.

P (r , t ) + . j (r , t ) = 0 . (4)
t

in 3-d

The above equation is called the Equation of Continuity and it describes the conservation of
probability in a region.
Note: In the above derivation, we initially considered a single particle, such as an electron. But,
experiments often involve beams of particles, for example, a beam of electrons from an
accelerator fired at an atom. If the beam is not too intense (i.e. the particle density is not too
high) each electron interacts with the atom independently of the presence of the other
electrons, and the interactions between the electrons are negligible. This means that we may
describe the problem involving the beam of electrons in terms of the same Schrodinger
equation that describes a single electron moving in the potential produced by the atom.
Analogous to equation of continuity in quantum mechanics, in classical physics we have

+ . j = 0 , where j = v and v is the velocity. For example,

t

In Fluid mechanics, mass density of a fluid and j = v mass flow density.

Equation of continuity describes the mass conservation for a volume element in a fluid (i.e.
mass can not be created or annihilated in a given volume.)

In Electrodynamics, space charge density in a conducting medium and j = v electric

current density.
Equation of continuity describes the charge conservation in a volume element in a
conducting medium (i.e. charge can not be created or annihilated in a given volume.)

Re * and here = = v and * is the

im
m
im

position probability
density
=
j
position probabilty density velocity = Pv .

Note: It can be written that j (r=
, t)

As seen in the case of a classical fluid, prob. density velocity should give probability (of
finding particles) flux through a unit area per unit time in a beam of particles. This fact

shows that it is reasonable to interpret j (r , t ) as the probability current density.
Consider

P(r , t ) + . j (r , t ) = 0 .
t

The integral form of this equation over a finite volume V surrounded by a surface of area S


P
(
r
,
t
)
d
V
+

t
. j (r , t ) dV =0 .
V
V

45

Greens theorem,

(. j ) dV =
j .dS

P(r , t ) dV +

t V

j .dS =
0

Physical Interpretation:

In a region where there are no sinks or sources, any decrease (increase) in the probability with time
in the volume V is accounted for by a probability current directed out of (into) it.
Now set

V
S

r
0 (as required by the square-integrability)

j 0.

P(r , t ) dr =
0.

t all

space

Note: The above result has been obtained only by using the definition of position probability
density and the TDSE (Schrodingers theory).

Solutions of the TDSE

(r , t )
i
t

Assume V to be time-independent.
Then, the TDSE has a solution of the form

2 2

+ V (r , t ) (r , t )

2m

V (r , t ) = V (r )

(r , t ) =
(r ). f (t ) .

Using the method of separation of variables, we get

2
f (t )

i ( r )
f (t ) 2 (r ) + f (t ) V (r ) (r )
t
2m

Dividing throughout by (r ). f (t )
1 f (t )
f (t ) t
Function of
t only
i

1 df (t )
f (t ) dt

From (1),

Solution

From (2),

2 1
1

2
=

constant (E , say)
(r ) +
V (r ) (r ) =
(r )
2m ( r )

Function of r only
1 2 2

(r ) + V (r ) (r ) =
E . (2)

( r ) 2m

E . (1)
df (t )
dt

= E f (t )
f (t ) =

df (t )
=
dt

constant eiEt

2 2

+ V (r ) (r ) = E (r )

2m

e iEt

iE
f (t )

(choosing, constant = 1)

or

H (r ) = E (r )

46
The above equation is called the Time-Independent Schrodinger Equation (TISE).

To get the solutions to TISE, one must know what V (r ) is, and it is a characteristic of the problem
under investigation

Consider the TISE,

H (r ) = E (r )
Since H is the total energy operator, the above equation is also the energy eigenvalue equation.

energy eigenfunction,
E energy eigenvalue
(r )
Since H is Hermitian, E must take real values only.

Operate H on (r , t ) =
(r ).ei E t

H (r , t ) =H (r ).ei E t

H (r , t ) =E (r , t )

, and by using the fact that H is time-independent,

=ei E t H (r ) =E ei E t (r ) =E (r , t ) .
Another form of the energy eigenvalue equation.

Position probability density,

* (r , t ) (r , t ) =
P(r , t ) =
* (r ).ei E t (r ).ei E t

Position probability density of (r , t ) =

(r ).ei E t
are called stationary states.

=
* (r ). (r ) =
P(r )

is constant in time. Such states

Consider the TISE,

H (r ) = E (r ). In general, TISE will have many energy eigenvalues

En with the corresponding energy eigenfunctions n (r ) .

E1

i.e.

1 (r ),

E2

2 (r ),

TISE can be written=

as
H n (r )

3 (r ),

E3

=
En n (r ) with n

................, etc, so that, the

1, 2, 3, ........... .

The corresponding solution to TDSE,

=
n (r , t )

i En t
with n 1, 2, 3, ...................
n (r ).e=

a particular solution

The most general solution

(r , t ) =

cn n (r , t )

cn n (r ).ei E t
n

n
n

Since we want (r , t ) to be normalized to unity, the complex numbers c n are chosen so that

cn

= 1.

Properties of Energy Eigenfunctions

Basically, there are two kinds of energy eigenfunctions.

(i)

Corresponding to bound states.

e.e.fns vanish at infinity. i.e. they can be normalized (square-integrable)

47
e.e.vas form a discrete set.
(ii)

Corresponding to unbound (scattering) states.

e.e.fns are only finite at infinity. i.e. they can not be normalized (not squareintegrable)
e.e.vas form a continuous set (continuum).

Note: In case (ii), the difficulty of normalization can be avoided by enclosing the system in a very
large (but finite) box with impenetrable walls.

* dx

* dx

= a

can not be normalized to unity.

1

is normalized to unity.
a
(L is chosen to be very large and hence, a may be large but finite)

Under the above box normalization procedure, the energy spectrum will become descrete. As
shown before, all the e.e.fns can be assumed to be normalized to unity.
Since H is a Hermitian operator, e.e.fns corresponding to different e.e.vs (non-degenerate) are
orthogonal. When an e.e.v. is degenerate, it is still possible to make the e.e.fns orthogonal by using
some orhogonalization procedure.

Therefore, we can expect in all cases, the e.e.fns to form an orthonormal basis. i.e. they

satisfy the condition m* n dr = m n .

all
space

Solutions to TISE for a Particle Moving in Various Potential Regions

(1) Free Particle (1-d)
Consider a particle of mass m and total energy E moving along the x-axis in a region of constant
potential energy.
=
V ( x)
V0 ,
< x <
dV ( x)

Force acting on the particle, F ( x) =

0.

=
dx
Choose V 0 = 0. (this choice will not affect the e.e.vas). Apply the TISE for the particle.
2 d 2 ( x)

+ =
< x <
V ( x) ( x)
E ( x),
2
2 m dx
2 d 2 ( x)

=
E ( x) .................. (1)
2m dx 2
p2
p2
Total energy,
E =
+ V ( x) =
2m
2m

p = k

p x = k x

E=

h2 k 2
2m

+ 0

p = k
k2 =

2mE
2

(dropping x)

48

d 2 ( x)
2

2mE

dx

Solutions (particular) of TISE,

( x)

=
0

( x) = e

d 2 ( x)

ik x

dx

+ k 2 ( x) =
0

For physically acceptable solutions (i.e. (x) 0 as x ), k has to be real E 0.

i.e. the energy spectrum of the particle is continuous and is extending from E = 0 to E = + .
Then, a general solution to TISE is
constants.

( x) = Ae+ i k x

+ Be i k x , where A and B are arbitrary

Solutions (particular) of TDSE are (x, t ) = e i k x e i E t .

General solutions to TDSE is ( x, t ) =
Ae i k x e i E t

Ae i ( k x t )
( x, t ) =
= 1 ( x, t )

+ Be i k x e i E t .

+ Be i ( k x + t ) , where E = .
+ 2 ( x, t )

The solution is a sum of two plane waves traveling in +x and x directions. Each wave represents a
particle moving in +x-direction with a precisely known linear momentum p = k ( p =
0 ) and xdirection with a precisely known linear momentum p = k ( p =
0 ).
When the amplitude of one of the plane waves in (x, t) is zero, B = 0 (say).
( x, t ) =
1 ( x, t ) =
Ae i ( k x t )
Consider normalization of (x, t).

Case (i):

( x, t ) dx =
A .
1 ( x, t ) dx =
A dx =

not normalizable.

Plane waves are not normalizable.

Consider the position probability density associated with (x, t).

P ( x, t ) =
( x, t )

=
1 ( x, t ) =
A = constant

Position of the particle moving in the +x direction is completely unknown on the xaxis.
x =

This is a direct consequence of the H.U.P, x.px 2 (As p x 0 x )

Consider the probability current density associated with (x, t)
*

( x, t ) ( x, t ) * ( x, t ) ( x, t )

2mi
dx

dx

p
k
2
2
=
A=
A = velocity p.p.d.
m
m
Similar results can be obtained when A = 0 in the general solution of TDSE.
j ( x, t )

49
Case (ii): When the amplitudes of the two plane waves are equal, i.e. A = B.

( x, t ) =
A e ik x

+ e i k x e i t

= C cos k x e i t

A standing wave whose nodes fixed at values xn =

( 2 + n ) k , n =
0, 1, 2, ........
P ( x, t ) =
( x, t )

=
C cos 2 k x

j ( x, t ) = 0

(show this)

When the amplitudes of the two plane waves are equal, the probability flux associated with
one plane wave is cancelled by that of the other. This makes the prob. per unit time that the
particle will cross a point x is zero. Therefore, the resulting standing wave represents a
particle moving along the x-axis with precisely known momentum ( k ) but whose direction
is unknown. Since P = 0 at x = x n , the particle can not be found at these points. This is due
to an interference effect between the plane waves.
To obtain information about the position of a particle localized within a region x, we must
superpose plane wave solutions of the form A(k ) e (

i k x (k ) t )

with infinitesimally different k

values to from a wave packet.

When k is continuous, (x, t) =

A(k ) e (

i k x (k ) t )

dk

all k
values

When k is discrete,

(x, t) =

A ( k ) ei( k x ( k ) t )
k

(2) Step Potential

Consider a particle of mass m and total energy E approaching from the left of the potential
0 x<0
V ( x) =
V0 x > 0

step which is defined as

Real potential
situation

x<0

V0

x>0

50
Since V(x) has a discontinuity at x = 0, we divide the region into two parts and solve TISE in
regions I and II separately. We have to consider two cases,
(a) E < V 0
Case (a):

(b) E > V 0

0 < E < V0

In region I, the k.e of the particle

= E 0 = E

In region II, the k.e. of the particle

= E V0 < 0

Classically, the particle should be reflected back to region I at x = 0. i.e. x > 0 is a classically
forbidden region.
In region I
When V ( x) = 0
2 d 2
I ( x) = E I ( x)
2 m dx 2
d2

2mE

( x) +
2 I

0
I ( x) =
dx
2
General solution to TISE
2m E
I ( x) =
A eik x + B e ik x , where k 2 =
2
General solution to TDSE

i (k x t )
Ae

I=
( x, t )

+ Be

represents incident
particles

(k x + t )

represents reflected
particles

In region II
When V ( x) = V0 ,
2 d 2
E II ( x )
II ( x ) + V0 II ( x ) =
2m dx 2
d2

2m

dx

( x)
2 II

(V0 E ) II ( x )

0
=

General solution to TISE

2m (V0 E )
.
II ( x ) =
C e x + D e x , where 2 =
2

General solution to TDSE

51
Ce x i t

II=
( x, t )

+ D e x it (Note: These are not plane waves.)

Since II ( x) has to be finite (small) in region II, e+ x is not acceptable.

Ce x

So, D 0
=
II ( x )

x > 0

To determine A, B and C. we apply boundary conditions which govern the continuity of wave
function in regions I and II, because they represent the same particle.

smooth joining

not joining

not smooth joining

Consider for smooth joining of a wave function

d

I ( x) x 0=
II ( x) x 0
I ( x) x 0 =
II ( x) x 0
=
=
=
dx
dx
A + B =
C

i k ( A B) =
C

ik +
B =
A
ik

2i k
=
A
ik

A, B and C are the amplitudes of the incident, reflected and transmitted waves respectively.

i k + i k x
, x < 0
e
ik

I ( x ) =+
A ei k x

II ( x )

2i k x
A
,
e
ik

x > 0
A

Intensity of the reflected wave = B * B = B

Intensity of the incident wave = A * A =

Reflection is total (100%).

(a standing wave)

(an exponentially decaying function)

ik +
=
A
ik

i k + i k +
2
=

A
i k i k

52
i.e., all the particles reaching the potential step with total energy E < V0 bounce back.
This result is in agreement with the prediction of classical mechanics according to which all the
particles with total energy E < V0 are reflected by the step.
Ce x

Now consider
II ( x)
=

=
p. p. d.

( II ( x)

x > 0

=
II* ( x). II ( x)

C 2 e2 x

0)

There exist finite probabilities of finding the particle in the classically forbidding region
( x > 0 ). This result is different from that is predicted by classical mechanics. This nonclassical phenomenon is called the penetration of classically forbidden region or tunneling.

Note:
Penetration doesnt mean that the particle is stored in region x > 0 permanently, because we see
that the incident particle is definitely reflected from the step.
Eg: Step potential is an approximation to the potential on a conducting electron moving near the
surface of a metal. Potential energy for an electron whose total energy is E increases at the
surface from a constant interior value (may be zero) to a higher constant exterior value V r
and E < V r . For Cu, V r E ~ 4 eV.
Flux of the incident beam of particles, ji=
Flux of the reflected beam of particles, jr=

ref

v=

Reflected flux in region I

=
Incident flux in region I

R
Reflection coefficient,=

inc v=

k
m

jr
=
ji

k
m
2

B
=
2
A

Reflection is total (100%).

Ce x

=
II ( x )

x > 0

II ( x ) decreases very rapidly as x increases. So the particle does not penetrate very far into the
classically forbidden region.
When x
Therefore

x =

, e2 x

the

0.

probability

2 m (V0 E )

is

appreciable

only

over

penetration

depth

53

inc

ref
=
II ( x )

Ce x , x > 0
x

A standing wave

inc and ref have equal amplitudes and velocities so they are in phase. Superposition of inc
and ref will result in a standing wave.
When V 0

Case (b):

II ( x) 0
No particle can penetrate into the classically forbidden region (i.e., an
impenetrable wall)

E > V0

In region I, the k.e. of the particle

= E 0 = E

In region II, the k.e. of the particle

= E V0 > 0

Classically, the particle will transmit into region II and no reflection is possible.
In region I, the solution of TISE has the same form as in case (a)
2m E
A eik x + B e ik x , where k 2 =<
x
0
I ( x) =
2

represents incident
particles

represents reflected
particles

In region II, TISE reads

General solution

2 d 2
II ( x ) + V0 II ( x )= E II ( x )
x > 0
2 m dx 2
2m
d2
0
( x) +
( E V0 ) II ( x ) =
2 II
dx
2

2m ( E V0 )

E ei k x + F e i k x , where k 2 =
II ( x ) =
2

represents transmitted
particles

represents reflected
particles

54
In region II, the potential energy remains constant at V 0

No reflection is possible.

F=0

=
II ( x )

E ei k ' x , x > 0

To determine A, B and E, apply boundary conditions.

d
d
( x)
I ( x) x 0 =
II ( x) x
=
=
dx
dx

( x)

I
II
x 0=
x 0
=

=
A + B

=
k ( A B)

k k
B =
A
k + k

k k i k x

e
k + k

A ei k x +
I ( x) =

II ( x )

2k i k x
A
e
k + k

k E

2k
E =
A
k + k

x < 0

x > 0

(a standing wave)

(a pure traveling wave)

B 0 indicates that some particles are reflected at x = 0.

This is again a result different from that is predicted classically.
Incident probability flux,

=
ji

Reflected probability flux

=
jr

Transmitted probability flux

jt
=

k
m
k
m

k
m

Reflection coefficient,
Reflection coefficient, R =

=
R

jr
=
ji

Reflected flux in region I

Incident flux in region I
k
2
B
m =
k
2
A
m

k k
=

k + k

1 +

V
1 0
E
V
1+ 0
E

55
Transmission Coefficient, T

=
T

Transmitted flux in region II

Incident flux in region I
k 2
E
jt
4kk
m
=
=
k 2
ji
( k + k )2
A
m

R < 1, T < 1 R + T =
1 , as required by the conservation of the # of particles.

Incoming flux = Transmitted flux + Reflected flux

Eg: This situation is an approximation to the potential acting on a neutron near the nuclear surface.
If the neutron gets energy so that E is a little greater than V 0 there is a probability for it to be
reflected back into the nucleus and thereby increasing the stability in it.

(3) Barrier Potential

V
V ( x) = 0
0

Consider V(x) defined as

in the region 0 x a
in regions x < 0 and x > a

V(x)
V0
I

II

III
x

0
a
A particle of mass m and total energy E is approaching the barrier from the left.
There are two cases.
(a) E < V 0

c.m. predicts a total reflection.

(b) E > V 0

c.m. predicts a total transmission.

For cases (a) and (b), the solutions to TISE in regions I and III are the same as those in the case of
free particles.
ik x

ik x

2m E

I ( x) =
Ae 1
+ B e 1 ......... (1), where k12 =
x < 0
2

ik x

ik1 x

III ( x ) =
Ce 1
+ De

2m E
x > a
.......(2) , where k12 =
2

56
when E < V 0

=
II ( x )

F e x

+ G e x ........... (3), where

=
2

F ei x

+ G ei x ........(4), where
=
2

2 m (V0 E )

when E > V 0

II=
( x)

2 m ( E V0 )
2

Since no reflection is possible in region III, D = 0

Note:

, 0 x a

, 0 x a

We cannot set G = 0, because x is finite when 0 x a .

We can not set G = 0, because a reflection is possible at x = a due to change in potential
energy.

Case (a) E < V 0

Consider equations (1), (2) and (3).
Appling boundary conditions at x = 0 and x = a,

I ( x) x 0=
=
II ( x) x 0 =
II ( x) x a =
III ( x) x a
=
d
I ( x)
dx
=
x

d
d
d
=
II ( x)
II ( x) x a=
III ( x) x
=
dx
dx
dx
x 0
0=

Obtain four equations and solve them to determine B, C, F and G in terms of A (Do this as an
exercise.)
In region I, the wave function is not a pure standing wave (since A > B) and has a small traveling
wave component.
In region II, the wave function is a standing wave with decreasing amplitude
In region III, the wave function is a pure traveling wave.

Reflection coefficient, R =

=
R

Velocity in region I = vI =

Reflected flux in region I

Incident flux in region I

vI
=
2
A vI

k
m

E
E
4

1

V0
V0

1 +

sinh 2 a

57

p.p.d

* ( x) ( x)
I

II

III

x
Minimum 0 (A > B)

Transmission Coefficient, T

Transmitted flux in region III

Incident flux in region I
2

=
T

C vIII
=
2
A vI

1 +

sinh 2 a
4E
E

V0
V0

vI
since =

v=
III

In this case (E < V 0 ), T is more important than R, because it is not expected classically.
Classically we expect R = 1, T = 0.
But quantum mechanically, T 0 The particle has a certain probability of penetrating the
barrier and appear in the x > a region even when E < V 0.
This phenomenon is called the Barrier penetration or Tunnel effect.
*
*

As E 0 T 0.
lim
=
T
E V0

mV0 a 2
1 +

2 2

Here

mV0 a 2
2

is a measure of the opacity

of the barrier.
*

In the classical limit, the opacity is very large. i.e. T = 0 for all 0 < E < V 0 .

When a 1 , T

16 E
E 2 a
1
e
V0
V0

T is very small.

Some consequences of barrier penetration (E < V 0 )

The emission of particles from radioactive nuclei (U238) through the potential barrier that they
experience in the vicinity of the nuclear surface.
Between A and B, an - particle of total energy E ~ 4 MeV must penetrate the nuclear potential
barrier. (E < V 0 )

58
V(x)
V0

4 MeV

Case (b): E > V 0

Consider equations (1), (2) and (4).
Apply boundary conditions at x = 0 and x = a to determine B, C, F and G in terms of A. (Do this
as an exercise) You will find that the wave function is oscillatory in all three regions.
Reflected flux in region I
Incident flux in region I

Reflection coefficient, R =

=
R

B vI
=
2
A vI

4E E
1

1 + V0 V0

2
sin a

vIII
=
A vI

Transmission coefficient, =
T

sin 2 a
1 +

4E
E

1
V0
V0

vI
since =

v=
III

In this case (E > V 0 ), R is more important than T, because classically we expect T = 1 and R = 0.
Since R 0, the particle has a certain probability of getting reflected back to x < 0 region.

(4) Infinite Square Potential Well (symmetric about at x = 0)

+

V(x)

II

III

a
m
a/2

+a/2

59
A particle of mass m is confined (trapped) to a potential well of width a which is defined as
0
V ( x) =

in the region
elsewhere

a/2 x + a/2

The walls of the well are impenetrable for the particle and therefore it is bound.
TISE will have solutions only for discrete values of energy.

(x) must vanish in regions I and III, because no penetration is possible.

=
I ( x) =
III ( x ) 0

we have to solve TISE only in region II

2 d 2
=
( x)
2m dx 2

E ( x ) ,

General solution,
Ceikx

( x)
=

+ Deikx ,

where
=
k2

= A cos kx + B sin kx

(x) must be continuous

( ( x)

a/2 x +a/2

2mE
2

II ( x) )

( a / 2

x + a / 2)

requires that, (x) = 0 at x = a/2

Since the potential makes an infinite jump at the boundaries

a
ka
ka
0
x =
A cos
,
B sin
=
2
2
2
a
ka
ka
=
At x
,
A cos
+ B sin
= 0
2
2
2

d
( x) need not be continuous.
dx

At

A cos

ka
= 0,
2

B sin

We cant make both cos

ka
= 0
2

ka
ka
= 0 and sin
= 0 for a given value of k. Also we cant choose
2
2

both A = 0 and B = 0, because, then (x) = 0. Therefore, we consider two classes of solutions.
1st Class
ka
= 0
2
n
,
n
=
2

B = 0 and cos
ka

=
2

1, 3, 5, .......

Wave function
=
( x)

A cos kx
=

n x
,
a

A An

n ( x)

An cos

=
k

A
cos kn x
=

n
kn
a
n x
A cos
a

(say)

60
+

To find A n , normalize n (x)

( x ) 2 dx = 1 .

set

a / 2

An

I ( x) 2 dx

+a / 2

a / 2

a/2

n x
cos 2
dx
=
a

a / 2

n ( x)

An

1
2

dx

+a / 2
a/2

2n x

1 + cos
dx
a

a / 2

2nd class
A = 0 and sin
ka

=
2

ka
= 0
2
n
=
,
n
2

n 2 2 2
, n
=
2ma 2

2, 4, 6, .......

An

2
n x
=
cos
, n
a
a

=
n ( x)
Wave function (energy eigenfunction),
Energy eigenvalue,
En
=

III ( x) 2 dx =
1
a
2

= 1

An =

2
.
a

1, 3, 5, .............

1, 3, 5, .........

n
kn (say)
a
2
n x
sin
,
n
2, 4, 6, .............
=
a
a
k
=

n ( x)
Wavefunction (energy eigenfunction)
=

(n = 0 does not represent a physically meaningful solution.)

Energy eigenvalues
En
=

n 2 2 2
, n
=
2ma 2

2, 4, 6, .........

By combining the two classes of solutions

Energy eigenfunctions
=
n ( x)
=
n ( x)

Energy eigenvalues =
En

2
n x
=
cos
,
n 1, 3, 5, .............
a
a
2
n x
sin
,
=
n
a
a

2, 4, 6, .............

n 2 2 2
=
, n 1, 2, 3, 4, 5, 6, .........
2ma 2

The above results are different from the classical prediction, according to which all the values of
energy are possible for the particle.
In the previous applications of TISE, there were solutions for every value of energy (a continuum).

Energy spectrum consists of an infinite no. of discrete energy levels (quantized levels) ranging from

2 2 2ma 2 to corresponding to bound states.

Energy levels are non-degenerate, i.e. for each energy eigenvalue there is only one energy eigenfunction.

Energy eigenfunctions n (x) and m (x) corresponding to Energy eigenvalues E n and E m (m n) are
orthogonal. i.e.

+a / 2

a / 2

* ( x) (x)dx = 0 .
n
m

61
Since each energy eigenfunction is normalized to unity, i.e.

+a / 2

a / 2

have

+a / 2

a / 2

* ( x) (x)dx =
n
m
nm

* ( x) (x)dx = 1 for any n, and we

n
n

energy eigenfunctions from an orthonormal set.

Lowest energy (zero-point energy) is not zero which is the case expected classically.

n 2 2 2
, n
=
2ma 2

Consider En
=

1 E1
n =

=Emin

1, 2, 3, 4, 5, 6, .........

2 2
=
2ma 2

0 (zero-point energy)

This is in agreement with the H.U.P, because

x. px
=
k.e.

px2
2m

x ~ a px ~ / a ,

and

2
2ma 2

E ~

px ~ px

px ~ / a

2
2ma 2

The total energy predicted by the H.U.P is of the order of the zero-point energy.
=
En

n 2 2 2
2 m a2

=
n2

2 m a2

2 2

En , =
n 1, 2, 3, 4, ...........

n2
16

n=4

n=3

n=2

n =1
a/2

+a/2

a/2

+a/2

62
Mathematically, f ( x) =
f ( x)

f ( x) = f ( x) -

a symmetric (even) function

an anti-symmetric (odd) function

Parity: the oddness or evenness of wave function

Eigenfunctions of the=
1st class, n ( x )

n ( x) =
n ( x)

nd
Eigenfunctions of the 2=
class, n ( x )

1, 3, 5, ......

even functions of x or even parity states

2
n x
sin
, n
=
a
a

n ( x) = n ( x)

2
n x
cos
, n
=
a
a

2, 4, 6, .....

odd functions of x or odd parity states

Classically, the particle is found with equal probability anywhere inside the well, but not so
quantum mechanically.

As n , we expect to have a constant probability of finding the particle inside the potential
well, which is the classical result, a result that confirms the correspondence principle. As a
increases, the spacing of the energy levels decreases. We get these energy eigenfunctions of
definite parity (even or odd) because the potential energy function is symmetric about x = 0,
i.e. V ( x=
)

V ( x) - Even (symmetric) function of x

Ex: Show that, when V ( x=

)

V ( x) , both (x) and (x) are solutions to the TISE with the same energy

eigenvalue E.
Assume that (x) is a solution to the TISE with the corresponding eigenvalue E.

2 d 2
E ( x)
( x) + V ( x) ( x) =
2m dx 2
Changing x x and using the fact that, V ( x=
)

V ( x) ,

2 d 2
( x) + V ( x) ( x) =
2 m dx 2

(x) is a solution to the TISE with the same eigenvalue E.

E ( x)

Consider the two cases,

(i)

the eigenvalue E is non-degenerate

i.e.(x) and (x) then differ only by a multiplicative constant so that ( x) =
( x)
eigenfunctions (x) have a definite (i.e. odd or even) parity.

(ii)

the eigenvalue E is degenerate

63
i.e. there can be more than one linearly independent eigenfunction corresponding to the eigenvalue
E. If these eigenfunctions (x) and (x ) do not have a definite parity, then it is possible to
construct two linear combinations of them such that each has a definite parity. For example,

e=
( x)

1 [ ( x )
2

+ ( x)] and o =
( x)

1 [ ( x )
2

( x)] are even and odd parity states

having the same eigenvalue E as ( x) and ( x) do. (Note:

=
( x) e ( x) + o ( x) and

( x=
) e ( x) o ( x) )

Parity Operator,
which has the property of changing x to x (or x to x) in everything that it
Consider the operator
acts on.

( x) =

( x)

(r ) =

(r ) ,

or

( x) =

( x)

(in 1-d)

( x, y , z ) = ( x, y , z )

(in 3-d)

is called the parity operator and its operation is equivalent to a reflection through the origin.

( x2 + 2x) = (x)2 + 2(x) = x2 2x

eg:
and it is defined by what it does to a function.
Note: There is no algebraic form of
For n particles, the definition of parity operator reads,
( x1 , x2 , x3 , ........., xn ) = ( x1 , x2 , x3 , ........., xn )

(r1 , r2 , r3 , ........., rn ) = (r1 , r2 , r3 , ........., rn )

(in 1-d)
(in 3-d)

Properties of
2 =I (i)

Unit operator

( x) =

( x)

Pf:

) ( x)
(

= ( x)

(
( x) ) =
( x)

2 ( x) = ( x) = I ( x)

are 1
(i) The eigenvalues of
( x) =

( x)

Pf:

(
( x) ) =

I ( x) = 2 ( x)

2 = 1

( x) =

( x)

= 1

=
1

( x)

the eigenvalue equation

2 ( x) =

( x)

( x) = 2 ( x)
1.

( x) =
( x)

( x) = ( x)

( x) =
( x)

even parity (symmetric) state, e ( x)

odd parity (symmetric) state, o ( x)

2 =I .

64
Ex:

Prove that,

is a hermitian operator
(a)

anti-commutes with x and p x , commutes with H , when V ( x=

(b)
)
=
H

A commutes with B

A anti commutes with B

p x2
+ V ( x )
2m

V ( x) and

=

AB
BA

=

AB
BA

commutes with H , i.e.
Note: Since
0 , we can find a set of simultaneous
, H =

and H .
eigenfunctions of
are orthogonal to each other.
(c) The odd and even parity states of

(5) Infinite Square Potential Well (not symmetric about x = 0)

Consider a particle of mass m confined to a potential well of width a which is defined as
in the region 0 x a
elsewhere

0
V ( x) =

V(x)

II

I(x) = 0

III

II(x)

III(x) = 0

m
a

Since the walls at x = 0 and x = a are impenetrable for the particle =

I ( x) =
III ( x ) 0 .
Solve TISE for the particle inside the potential well.
2 d 2
=
( x)
2m dx 2

E ( x ) ,

d2
dx

( x) + k 2 ( x) =
2

General Solution,
=
( x)

0 x +a

0,

k2 =

A cos kx +

( ( x)

II ( x) )

2mE
2

B sin kx

0 x a

Apply the boundary condition ( x) = 0 at x = 0 and x = a. We need not worry about the
continuity of d dx .

65
At x = 0 A = 0 ( x) = B sin kx,
0 x a
At x = a B sin ka = 0 ka = n k = n a kn (say) , n = 0, 1, 2, ........
n = 0 does not represent a physically meaningful solution.

n ( x)
=

II (x) = 0

kn = 0

(n = 0

Bn sin

n x
,
a

for all x, 0 x a)

0 x a
+

To find B n , normalize n (x)

set

( x)2 dx = 1 .

Bn

I ( x) dx
2

n x
=
dx
sin
a
2

n ( x)
Bn

1
2

dx

a
a

1
0

cos

III ( x) 2 dx =
1

2n x
dx
a

n ( x)
Wave function (energy eigenfunction),
=
n 2 2 2
, n
=
2ma 2

Energy eigenvalue,
En
=

Bn

2
n x
sin
,
n
=
a
a

a
2

= 1

Bn =

2
.
a

1, 2, 3, .............

1, 2, 3, .........

2 2

n = 1, 1 (x)

E1 =

n = 2, 2 (x)

E 2 = 4E 1

n = 3, 3 (x)

E 3 = 9E 1

2ma 2

We get infinite no of discrete e.e values ranging from

2 2
2ma 2

to .

They are all non-

degenerate. (i.e. for each E value, there is only one (x) value )

We dont get two classes of solutions as V(x) is not symmetric about x = 0.

Zero-point energy,
=
E1

2 2
2ma 2

0 , as required by H.U.P.

Existence of zero-point energy is typical in all systems in which a particle is confined to move in a
limited region.
=
En

n 2 2 2
2 m a2

=
n2

2 m a2

2 2

En , =
n

1, 2, 3, 4, ...........

We can not talk of odd and even parity states as in the symmetric potential well case.

Classically the particle should be found with equal probability anywhere inside the well but
not so in quantum mechanics.

As n , the probability of finding the particle inside the well is almost constant.

66

n (x) from an orthonormal basis

n ( x) m ( x)dx

i.e.

= nm

The particle can not have an arbitrary energy values as expected classically. Instead, the

energy values are quantized. This situation occurs whenever a particle is confined to move
in a limited region in space.
Recall: no quantization of energy is possible for
1. Free particle
2. Potential step
3. Potential barrier
n2
9

n=3

n=2

n =1
a

*(6) Finite Square Potential Well

V ( x)
V

II

I
a 2

III

a 2

Consider a particle of mass m and total energy E bound to the potential well (i.e. E < V 0 , and we are
interested in bound states only) which is defined as

67
V
V ( x) = 0
0

x < a 2 or x > a 2
a 2 < x < a 2

When E < V 0 , classically the particle can be only within the well and E can have any value between
0 and V 0 . The above potential can be approximated to the following physical systems.
Eg;

A neutron confined to the nucleus.

depth ~ 50 MeV

nuclear diameter ~ 10 14 m

The potential acting on a conduction electron in a metal due to closely spaced positive ions.

one ion

3 ions in line

Inside the well, the general solution to the TISE

=
II ( x )
=

A ei x

+ B e i x ,

where=
2

A sin x + B cos x

2m E
2

a 2 < x< a 2

Outside the potential well, the general solution to the TISE

I ( x)
=

C e x

+ D e+ x ,

III ( x ) =
E e x + F e+ x ,

2
where
=

2 m (V0 E )

, x < a 2

2 m (V0 E )
where 2 =
, x > a 2
2

For (x) to be finite outside the well (as x ),

Apply boundary conditions: (x) and

C = 0, F = 0.

d ( x )
are continuous at x = a 2 .
dx

x = a 2,

A sin ( a 2) + B cos( a 2) =
D e a 2

D e a 2
A cos ( a 2) + B sin( a 2) =

x = a 2,

A sin ( a 2) + B cos( a 2) =
E e a 2

E e a 2
A cos ( a 2) B sin( a 2) =

We get,

68
2 A sin ( a 2) = ( D E ) e a 2 ....... (1) ,
2 A cos ( a=
2)

2 B cos ( a =
2)

( D + E ) e a 2 .......... (2)

2 B sin ( a=
2)

( D + E ) e a 2 ......... (4)

( D E ) e a 2 ........... (3) ,

If A 0 and ( D E ) 0, Equ n s (1) and (3)

cot ( a 2) = ....... (5)

If B 0 and ( D + E ) 0, Equ n s (2) and (4)

tan ( a 2) =
......... (6)

Since equations (5) and (6) can not be valid at once and we do not want all A, B, D and E to vanish,
Note: In this problem, V(x) = V(x)

we have to look for two classes of solutions.

For the 1st class: =
A 0,
=
D
For the 2nd class:

E and

tan ( =
a 2)

............. (6)

B =
0, D =
E and cot ( a 2) =
....... (5)

When A = 0 and D = E, from the expressions of I ( x) , II ( x) and III ( x) , we see that the
resulting eigenfunctions are even (symmetric) functions of x.
When B = 0 and D = E, from the expressions of I ( x) , II ( x) and III ( x) , we see that the
resulting eigenfunctions are odd (anti-symmetric) functions of x.
To find energy values of even and odd parity states, we have to solve equns. (5) and (6) with the
definitions of and using a numerical or a graphical method. Here we use the graphical method.

cot ( a 2) =

tan ( a 2) =

( a 2) cot ( a 2) =

a 2 cot

( a 2) tan ( a 2) =

a 2

tan

= ,

= ,

where = a 2 and = a 2 .
2

+ =

a2 2
( + 2=
)
4

a 2 2mV0
.
=
4 2

which is the equation of a circle of radius

mV0 a 2
2

2 + 2 =
R2 ,

R = mV0 a 2 2 2

1 2

and are restricted to positive values. So, the energy values of even and odd parity states may
be found from the points of intersections in the first quadrant of each of the curves tan = and

cot = plotted verses with the above circle.

We see that the allowed values of E, when E < V 0 are quantized. (when E > V 0 , allowed E values
form a continuum.)

69
The number of E values will depend on the radius

= tan

of the circle. Note that,

(1) The number of allowed energy values

depends on the product V0 a 2 and not on V 0

3
2

and a separately.
(2) At least one even parity state is guaranteed
to exist. (No matter how small R is, the
circle intersects tan = curve.)
(3) The ground state is an even parity state.

= cot

The 1st excited state gives an odd parity

state. The 2nd excited state gives an even parity state.
(4) To have the 1st odd parity state, it requires R 2

V0 a 2

2 2
2m

(5) There exist only a finite number of discrete bound states.

For solutions of the 1st class, A = 0, D = E. To find the arbitrary constants, normalize (x) .
Set

n ( x ) 2 dx = 1

a / 2

D 2 e 2 x dx +

a/2

B cos 2 x dx +

1
E e 2 x dx =

a/2

a / 2

B
sin a
e a
+
a+
=
1

2
2

a
a
= De
2

With this, use B cos

to get B and D. Similarly, find the normalization constants

for the other class of solutions.

E

3
VO

1st class

2nd class

E3

even

E2

odd

x
1

1st class

E1

a
2

a
2

even
a

70
Eigenfunctions extend into regions outside the well. Classically, the particle could never be found
in these regions when E < V 0 . However, quantum mechanically, it is possible to find the particle
outside the well and it moves further out as E increases.

(7) Linear Harmonic Oscillator Potential

Consider the 1-d motion of a particle of mass m attached to a fixed center by a force proportional to
the displacement.
Eg: a mass attached to one end of a spring
The restoring force, F x
dV ( x)
F =

=
kx
dx

F =

V ( x) =

kx , k = m 2 ,

1 2
kx (potential energy of a L.H.O)
2

x=0

x=x

Classical mechanics predicts, the oscillating frequency

Total energy, E x , < x <

k - force constant

V(x) =

1
2

k
m

0<E<

(continuous).

1 2
kx
2

The importance of L.H.O. potential is that any arbitrary potential can be approximated to a L.H.O.
potential in the vicinity of a stable equilibrium position.
Consider any function W ( x) that has an equilibrium position at x = a.

71
W(x)

Equilibrium position
x

Taylor series expansion of W ( x) about x = a can be given by

W (=
x)

W ( a ) + ( x a )W ( a ) +

1
( x a )2 W ( a ) + ......
2

( x a) ~ 0

For x values in the vicinity of x = a,

higher order terms can be neglected.

Since W ( x) has a minimum at x = a

d 2W

dW
= 0,
dx x =a

dx

> 0

W ( x) =

W (a) +

x =a

Now by choosing a new set of axes such that X = x a,

W (X ) =

1
KX 2 ,
2

1
( x a )2 W ( a ) + ......
2

W=
(X )

W ( x) W (a)

where K = W ( a )

L.H.O is a model for systems in which there are small vibrations about a point of stable
equilibrium. eg: Vibration motion of atoms in molecules and in solids.

TISE for a L.H.O reads

1 2
2 d 2
( x) +
kx ( x ) =
E ( x ) < x <
2
2 m dx
2

Solutions to this equation can be obtained with some difficulty. As it is going to be a time
consuming exercise, here we do not want to worry about it and we give only the final results.
The discrete set of energy eigenvalues are given by

En =n +

1
2

=n +

1
2

) h ,

n =
0, 1, 2, 3, ............

The corresponding normalized energy eigenfunctions are given by

72
12

2 2

e x 2 H n ( x ) , n
=

2n n !

n ( x)

where

14

12

m
=

mk
=
2

=
a1 2 , a

H n ( x ) - Hermite polynomial of degree n,

Since En =n +

1
2

=n +

1
2

0,1, 2, 3, ...........

) h ,

( 1)n e x

Hn ( x) =

dn
dx n

e x

n =
0, 1, 2, 3, ............

Quantum mechanical energy spectrum consists of an infinite sequence of discrete levels.

E0
=

1
=
2

1 h
2

3
=
2

,=
E1

3 h
2

,=
E2

1
2

1 h
2

5 h
2

= h .

Energy levels are equally spaced by the amount

Minimum (ground state) energy =

5
=
2

The existence of zero-point energy is purely a quantum mechanical phenomenon (as required by
the H.U.P)
Classically, the minimum energy = 0 (when T = 0 and V = 0). This occurs when the particle is at
x = 0,

rest (no oscillation) at the equilibrium position.

px = 0.

This tells us that we know the position and the linear momentum of the particle exactly at the same
time x = 0, px = 0

a contradiction to H.U.P

Total energy of the oscillator of amplitude A,

1
1
1
1
1
m 2 A2
=
( A )( m A ) = ( A ) px = x . px ~
2
2
2
2
2
Therefore, the energy of the lowest (ground) state is compatible with the H.U.P.

E
=

E=
n

(n

1
2

12

n ( x) =

2n n !

E0 =

1
2

E1 =

3
2

E2 =

5
2

E3 =

7
3 x
2 =

0 ( x)
1 ( x )

2 ( x)
=

( )

12

12

2
12

12

48

2 2

x 2

Hn ( x)

2 2

x 2

2 xe

2 2

x 2

( 4 2 x2 2) e x

2 2

(8 3 x3 12 x ) e x

2 2

73
V(x)

E4
E3
E2
E1
E0

n=4
n=3
n=2
n=1
n=0

Since V(x) is symmetric (even) function of x, we get two classes of solutions as n ( x) for the
TISE.

n ( x) =
n ( x) , when n = 0, 2, 4, . (even)
n ( x) = n ( x) , when n = 1, 3, 5, .. (odd)
The energy eigenvalues are non-degenerate. i.e. for a given value of n, there exists only one

n ( x) corresponding to E n ,
i.e. 0

E0 , 1 E1 , 2

E2 , .............. etc.

n ( x) from an orthonormal basis set. i.e.

n* ( x ) m ( x ) dx = n m

For a given state n ( x) ,

= n x n =

px

= n p x n =

n* ( x ) x n ( x ) dx = 0

n* ( x ) i

0
n ( x ) dx =
x

The above results can be obtained only by considering the symmetry of the system.
Also, for a given state n ( x)
V

= n

V n

= n

T n

1
1
= n* ( x) kx 2 n (x)dx = n +
2
2

2 d 2
= n* ( x )
2m dx 2

1
= En 0
2
2

1
n ( x ) dx = n +
2

1
2

= En 0
2

On the average, the total energy is equally shared by the potential and the kinetic energy.

74
Note:

An easy way to determine T

H = T + V

= T

) when

) is known.

En = T

1
2

En

= 12 En

Lets treat a particle subjected to L.H.O motion classically.

The position of the particle
The speed of the particle,
Total energy,

x(t ) = A sin t ,

=
v

A - amplitude of the oscillation.

A cos
=
t

E = T + V =

1 mv 2
2

A2 x 2
1 kx 2
2

1 m 2 A2
2

1 kA2
2

Classical turning points are given by E = V ( x) and they are located at A =

2E
, 0<E<
k

Quantum mechanical value of the total energy En =

n + 12 , n =
0, 1, 2, 3, ............
When E is chosen to be equal to En in the expression of A, we can obtain the amplitude (or turning
points) of the L.H.O whose total energy is equal to the quantum mechanically allowed values.

2 En
i.e. A =

An (say)
k
2E0
2 E1
3

, A1 =
, A 2 = .

A0 =
k
k
k
k
Quantum mechanically, the position probability density, Pn ( x) = n ( x )

Classical mechanically, the position probability density, Pc ( x) is defined as, the fraction of the
total time spent by the particle in a unit length element on the x-axis.
i.e.

P=
c ( x)

1v
=
T 2

2
=
Tv

2
2

A x

Quantum mechanical value of the amplitude, An =

1
2

A x

0< A<

2 En
k

To compare Pc ( x) with Pn ( x) , we replace A with An in the expression of Pc ( x) .

As it can be seen in the following figures, the eigenfunctions (or the corresponding probability
densities) do not fall sharply to zero at the classically turning points of the oscillator. However they
decrease very sharply. The amplitude of an oscillator is not sharply defined quantum mechanically
and as a result, there is a finite probability (i.e. non zero) of observing the particle outside the
classical limit. However, the particle is confined mainly to classically allowed region

75

P3(x) = 3

n=3
P2(x) = 2

n=2

Pc(x)

P1(x) = 1

P0(x) = 0

n=1

Pc(x)

n=0
x

As we can see, the general agreement between the classical and quantum results improves with
increasing n.

Algebraic Method for Obtaining the Energy Eigenvalues of a L.H.O

p 2
p 2
H = x + 12 kx 2 = x + 12 m 2 x 2 ,
2m
2m
Introduce the operators as done by Dirac.
i p x
m
a =
x
2
2 m

k
m

Using the facts that p x and x are hermitian operators and [ x , p x ] = i , it can be shown that
a+ = a ,
H
=

Ex:

a = a+

1
a )
a a+ =
( a a+ + a+ =
2
2
Verify the above results.

[ a ,

and

a+ a +

If is an eigenvector of H belonging to the eigenvalue E

H , a = a

Now, consider the state a .

=
H a

a+ ] = 1
1
2

and also H , a =

H = E

a H a

H a =
a H a

a is also an eigenvector of H corresponding to the eigenvalue

( E ) .

=
( E ) a

76
Since a+ raises and a lowers the value of E by the amount , they are called the raising and
lowering operators respectively.
Since H contains p x2 and x 2 terms, H in any state can not be negative. Therefore, the
eigenvalues of H must be non-negative.
If E0 is the smallest eigenvalue and 0 is the corresponding eigenvector (i.e.
= 0 . Otherwise, H a
H = E ), we must have a
= ( E ) a
0

would correspond to the eigenvalue ( E0 ) which is a contradiction.

Now, consider a+ a 0 .

H 0 = E0 0

=
0

E0 =

1
2

d
0 im x 0
dx

0 = A0 e

By integrating

m 2
x
2

0 =

d
0
dx

0
=

i p x
2 m

m
x 0

, where A 0 is to be determined via normalization

H a+2 0 =

( E0 + + + ) a+3 0

, H a+n
=
0

( E0 + + ) a+2 0
( E0 + n ) a+n 0 .

En , we get H n = En n .
n and ( E0 + n ) =

Taking a+n 0
=
En

1
2

m
x +
2

= 0 with =
a

Consider the operation of a+ , n times on 0 .

= ( E + ) a ,
H a
+
a+3

H 0 =

----------- Zero-point energy

To find the energy eigenfunction 0 , use a 0

a+ a =
0

a 0 = 0

( H 12 ) 0

( H 12 ) 0

E0 + n

E=
n

( n + 12 ) , where

n = 0, 1, 2, 3, ..............

The eigenfunctions of excited states are obtained by applying the raising operator.

n =

An a+n e

m 2
x
2

As we have seen, the raising and lowering operators generate new solutions to the Schrodinger
equation, but, these new solutions are not correctly normalized. Thus, a+ n is only proportional
to n +1 and a suitable normalization constant should be determined.
Let n

be a normalized eigenvector corresponding to the eigenvalue En and n +1

normalized eigenvector corresponding to the eigenvalue En +1 .

n +1 = Cn +1 a+ n , where Cn +1 is the normalizing coefficient.

be a

77

n +1 = Cn* +1 n a+

n + 1 n + 1 = Cn + 1

Since n +1 n +1

=
1

Cn + 1

C
=
n +1

Similarly, when n 1
Then, we have

a+ = a

= 1,

n a+ a+ n

and

a=
a+

H
1
+ n
2

H
1
+

=
1

Cn + 1

a+ 0=
, 2
=
1

n + 1 n +1 ,

1
a+ 1
=
2

1
2

( n + 1) n n

(assuming that Cn +1 as real and positive)

n +1

= Cn 1 a n , it can be shown that Cn 1 = 1

a+ n=

a n

, 3
( a+ )2 0=
=

1
n!

n . (verify this result)

n n 1 and hence
1
a+ 2
=
3

1
3.2

( a+ )3 0

( a+ )n 0

The eigenvectors n with n = 0, 1, 2, 3, .............. form an orthonormal basis, { n

m n

, .....

}.

i.e.

= m n .

*(8) The Periodic Potential (1-d)

Consider the motion of a particle of mass m in periodic potential of period l, which is defined as
V(x + l) = V(x). Such a potential with rectangular sections is called the Kronig-Penney potential. It
can be used as a model of the interaction to which an electron is subjected in a crystal lattice
consisting of a regular array of single atoms separated by the distance l.

Although a real crystal is of finite length, here we consider an idealized situation where x varies
along the entire x-axis in the potential energy function.
Since the kinetic energy term is unaltered by the change x x + l , with the above potential
energy function, the whole Hamiltonian is invariant under displacements by l. For the case of zero
potential, when the solution corresponding to a given energy E = 2 K 2 2 m is ( x) = ei K x , the
displacement yields

78

( x +=
l)

x +l)
ei K ( =
ei K l ( x) ,

which is the original solution multiplied by a phase factor, so that ( x + l )

observables will therefore be the same as at x as at x + l.

Therefore, all physically acceptable solutions must satisfy the relation

( x + nl ) =
ei n K l ( x) , with l K l and n = 0, 1, 2, ........

=
( x) . The

Bloch condition

If we write ( x) in the form

( x) = eiKx uK ( x)

uK ( x + l ) =
uK ( x) -

Blochs theorem

Bloch wave given by ( x) = eiKx u K ( x) represents a traveling wave of wavelength = 2 K

and amplitude u K ( x) which is periodic with the same period l as that of the crystal lattice.

Energy Bands
With the zero of the energy scale sitting at the top of the wells, consider the two cases for which the
electron energy E is such that V0 < E < 0 and E > 0 .

Case 1:
The TISE is

V0 < E < 0

d 2 ( x)
dx

dx

d 2 ( x)
where

=
2

+ 2 ( x) =
0,

inside the wells

2 ( x) =
0,

between the wells

2m
2

(V0 + E ) ,

Solving the two equations for a cell b l to b, we have

2 =

2m
2

E.

(=
x)

Aei x + Be i x ,

b l < x < 0

( x)=

Ce x + De x ,

0 < x < b

Blochs theorem shows that, the electron does not belong to any one atom (ion) of the lattice, but
has an equal probability of being found in the neighbourhood of any of the atom.
In the cell (b l , b), =
uK ( x)

Aei( K ) x + Bei( + K ) x
( iK ) x

.........(1) ,

b l < x < 0

( + iK ) x

........(2) ,
0 < x < b
u=
Ce
+ De
K ( x)
Since u K ( x) is periodic, the above equations determine u K ( x) (and hence ( x) ) for all values of
x.
In order to write u K ( x) in the region b < x < l , using the fact that u K=
( x)
uK ( x l )
=
uK ( x)
Aei( K )( x l ) + Bei( + K )( x l ) .........(3) ,
b < x < l
For solutions to be physically acceptable, ( x) and d ( x) dx (and hence u K ( x) and du K ( x) dx )
must be continuous at both edges of the potential well (then it holds true for all wells)
Equations (1) and (2)
A+ B = C + D,

79
i( K ) A i( + K ) B = ( iK )C ( + iK ) D ,

Equations (2) and (3)

Ae i( K ) c + Bei( + K ) c = Ce ( iK ) b + De ( + iK ) b ,
i( K ) Ae-i( K ) c i( + K ) Bei( + K ) c = ( iK )Ce ( iK ) b ( + iK ) De ( + iK )b ,
where c= l b .
From the above four equations, A, B, C and D can be determined. For a non-trivial solution, the
determinant of the coefficients A, B, C and D must vanish. This result in the condition
2 2
cos c cosh b
sin c sinh b =
cos K l ............... (4)
2
from which energy E can be obtained.

Case 2:

E > 0

In this case, becomes imaginary and this can be treated by setting = ik with k 2 =

2m
2

E.

Then for this case, the above condition can be rewritten as

2 + k2
cos c cos kb
sin c sin kb =
cos K l ................ (5)
2 k
Using the fact that the left-hand sides of the two conditions join smoothly at E = 0, one function of
E is required for the full energy range E > V0 .

F ( E ) = cos K l .
When the function F(E) is plotted for typical values of b, l and V 0 , it can be seen that

Plot of F(E), which represents the left-hand sides of equations (4) and (5) as a function of the energy E. The heavy lines show the
allowed values of E, corresponding to conduction bands; they are separated by forbidden energy gaps

Since K is real

cos Kl 1

Values of E for which F ( E ) >1 are inaccessible.

Allowed values of E fall into bands satisfying the condition F ( E ) 1 .

80
When the separation between the wells is increased, the energy bands for V 0 < E < 0 shrink and in the limit l contract into
discrete energy levels of an isolated potential well.

If the separation between the wells ( l ) is increased, keeping c or V 0 fixed

the energy bands for V0 < E < 0 become narrower and contract in the limit
l into discrete energy levels of an isolated potential well. Eg: a less
affected electron in an atom in the presence of the other atoms in a crystal.
Bands corresponding to the lowest-lying levels are the narrowest. Eg: most tightly bound electrons
are less likely to be perturbed by the presence of the other atoms.
Setting up of the boundary condition that = 0 at both ends of the 1-d crystal, i.e. electron can not
escape from the crystal, requires a standing wave solutions to TISE by the superposition of Bloch
waves (traveling).
not easy to implement
It is possible to apply periodic boundary conditions for a 1-d lattice forming a closed loop
containing N 1023 atoms. Single-valuedness of the wave function requires that,
(x + N l) =
( x)
ei n K l ( x)
( x + nl ) =

(shown before)

ei N K l = 1
K = 2 n N l , n = 0, 1, 2, .......

*The Scattering Potential

Consider the scattering of a particle by an arbitrary potential localized on a finite part of the x-axis
as shown below.

From the experience gained in previous applications, the general solutions to TISE in regions I and
III can be written straight away (consider unbound (scattering) states for which E > 0).
In region I ( V ( x) = 0 )

=
( x)

A ei k x + B e i k x ,

where k 2 = 2 mE 2

In region III ( V ( x) = 0 )

( x)
=

F ei k x + G e i k x ,

where k 2 = 2 mE 2

Since the potential is not specified in region II, we use the fact that TISE is a linear, second-order
differential equation.
In region II (V(x) is not specified) =
( x)

C f ( x) + D g ( x) ,

where f ( x) and g ( x) are any two linearly independent particular solutions.

81
From the four boundary conditions (two joining regions I and II, and two joining regions II and III), two can
be used to eliminate C and D and the other two can be solved for B and F in terms of A and G.

=
B

S11 A + S12 G

=
F

S21 A + S22 G .

The four coefficients Si j depend on k (and hence on E) and constitute a 2 2 matrix,

S
S = 11
S21

S12
called the scattering matrix or S-matrix. It gives the outgoing wave amplitudes
S22

(B and F) in terms of incoming wave amplitudes (A and G).

B
A
= S
F
G
Note: For Si j , the following conditions hold.

S11

+=
S12

S12

1,

+=
S22

*
*
S11 S12
+=
S21 S22

1,

For particles incident from the left, G = 0, so the reflection and transmission coefficients are
2

=
Rl

B
=
2
A

S11 ,

=
Tl

F
=
2
A

S21 .

For particles incident from the right, A = 0, so the reflection and transmission coefficients are
2

=
Rr

F
=
2
G

S22 ,

=
Tr

B
=
2
G

S12 .

The S-matrix tells us everything about scattering from a localized potential.

If there are any bound states (E < 0) in the problem under consideration, then ( x) has the form
=
( x)

Be x

C f ( x) + Dg ( x)

x
Fe

(Region I),
(Region II),
(R egion III),

with 2 = 2 mE 2 .
In this case, boundary conditions are the same as before, so the S-matrix has the same structure
(with k replaced by i ). But, A and G are necessarily zero whereas B and F are not, and hence at
least two elements in the S-matrix must be infinite. Therefore, if one has got the S-matrix for E > 0
and want to locate the bound states, put in k i and look for energy values at which the
elements of S-matrix become infinite.

82

Motion in Three-Dimension
(9) Free Particle (3-d)
Consider a particle of mass m moving in a region of potential energy

V ( r=
)
TISE

V ( x, y, z=
)

V
=
0 , in the region x , y , z .
0

2 2

(r ) + V (r ) (r ) =
E ( r )
2m

Assume a solution of the form ( r ) = x ( x ) y ( y ) z ( z ) and the corresponding energy

E =

2
2m

Ex + E y + Ez .

2 x ( x ) y ( y ) z ( z ) + 2 y ( y ) x ( x ) z ( z ) + 2 z ( z ) x ( x ) y ( y )

( Ex + E y + Ez ) x ( x ) y ( y ) z ( z )

Dividing throughout by ( r ) = x ( x ) y ( y ) z ( z ) and separating variables,

2 1
2
x=
( x)
2m x ( x ) x 2
Solution,

Ex

2
x

x ( x) +

(1-d case)
x ( x) =
0,

2mEx

i kx x
,
k x2
=
x ( x ) e=

Similarly, in y- and z-directions,

ik y

=
y ( y)

=
e y ,
k y2

=
z ( z)

=
e i kz z ,
k z2

2mE y
2
2mEz

The wave function ( r ) = e i k .r with k = k x , k y , k z

particle with energy E =

2mEx

and r =

( x, y , z )

describes a free

2 k 2

and linear momentum p = k .

2m

(10) Square Potential Box (3-d)

Consider a particle of mass m, confined to move in a rectangular potential box which is defined as
0
V ( x, y , z ) =

in the region 0 x a, 0 y b, 0 z c
elsewhere

83
z
c
b

Walls of the box are impenetrable for the particle outside the box, (r ) = 0 . Inside the box,

the wave function (r ) of the particle satisfies the TISE.

2 2
=
(r )
2m

E (r ) ,

( since V (r )

0 inside the box )

Assume a solution of the form ( r ) = x ( x ) y ( y ) z ( z ) and the corresponding energy

E =

2
2m

Ex + E y + Ez .

z
+

z
+
(
)
(
)
(
)
(
)
(
)
(
)
2 x
y
2 y
x
2 z ( z ) x ( x ) y ( y )
z
z
x

=
Ex + E y + Ez x ( x ) y ( y ) z ( z )

Dividing throughout by ( r ) = x ( x ) y ( y ) z ( z ) and separating variables,

2 1 d 2
=
x ( x)
2m x dx 2

Ex ,

0 x a

2 1 d 2
=
x ( y)
2m y dy 2

Ey ,

0 y b

2 1 d 2
=
z ( z)
2m z dz 2

Ez ,

0 z c

We get three TISEs for 1-d square potential wells placed in x-, y-, and z-directions.
Using the boundary conditions,
=
x ( x)

0=
at x

0, a,

=
y ( y)

0=
at y

0, b,

=
z ( z)

=
0 at z

0, c

As in the1-d case, the solutions to the above TISE can be written as

nx x
nx2 2 2
2
sin
Ex =
x ( x) =
nx ( x),
Enx , nx = 1, 2, 3, .........
a
a
2ma 2

y ( y) =

ny y
2
sin
b
b

n y ( y ),

Ey

n 2y 2 2
2mb 2

En y , n y = 1, 2, 3, .........

84
n z
2
sin z
c
c

z ( z) =

nz ( z ),

Ez

The normalized energy eigenfunction,

nx n y nz ( x , y , z )
=

nz2 2 2
2mc 2

Enz , nz = 1, 2, 3, .........

ny y
n x
n z
8
sin x
sin
sin z ,
abc
a
b
c

nx ( x) n y ( y ) nz ( z )
=

0 x a, 0 y b 0 z c

Corresponding energy eigenvalues,

Enx n y nz

2 2 nx2

Enx + En y + Enz =

2m a 2

n 2y

b2

nz2
, nx , n y , nz =
c 2

1, 2, 3, ........ Energy

spectrum is discrete. As the dimensions of the box increase, the spacing of the energy levels will
decrease

energy spectrum will become continuous.

A more interesting situation occurs when the box is cubical i.e. a = b = c

Enx=
n y nz

2 2 nx2

2m a 2

n 2y

a2

nz2

+ =
a 2

2 2
2ma 2

nx2 + n 2y + =
nz2

n 2 2 2
2ma 2

n2
The values of energy are determined by the value of n.
8

nx n y nz ( x , y , z ) =

a3

sin

ny y
nx x
n z
sin
sin z ,
a
a
a

Ground level of the particle occurs when, n x = n y = n z = 1 = n2

E111
=

2 2
2ma 2

111 ( x, y, z ) =

12 + 12 +=
12
8
a3

sin

x
a

sin

y
a

3 2 2
2ma 2
sin

z
a

Ground level is non-degenerate

For higher energy levels, we see that the states characterized by the combination of integers n x , n y
and n z which give the same value for n, will have the same energy. However, we get different
eigenfunctions (states).
n x = n y = 1, n z = 2
n x = n z = 1, n y = 2
n z = n y = 1, n x = 2

n2 = 6

85
E
=
112

E121
=

6 2 h 2

E
=
211

112 ( x, y, z ) =
121 ( x, y, z ) =

211 ( x, y, z ) =

8
a3
8
3

a
8
a

2ma 2

sin
sin
sin

x
a

x
a

sin
sin

y
a

sin

2 z
a

2 y
z
sin
a
a

2 x
y
z
sin
sin
a
a
a

Since E 112 = E 121 = E 211 but 112 121 211 , a degeneracy exists in the 1st excited level. The
degree of degeneracy = 3 (a 3-fold degenerate level).
The 2nd excited level occurs when n2 = 9, i.e. n x , n y , n z , taking values 1, 2, 2 or 2,1, 2 or 2, 2,1 and
it is also a 3-fold degenerate level.
Enx n y nz =

E/E 0

2 2 n2
2ma 2

E0
=

E111
=

=1

for the ground level

=2

for the 1st excited level

=3

for the 2nd excited level

3 2 2
2ma 2

= 11/3 for the 3rd excited level

=4

for the 4th excited level

4E0
11E0 3

3E0
2E0

dE

E0
E=0
Small box ( a = b = c )
E/E0

Large box

Q. numbers (x, y, z)
Deg. of degeneracy
(2, 2, 2)
1
(1, 1, 3), (3, 1, 1), (1, 3, 1)
3
(2, 2, 1), (2, 1, 2), (1, 2, 2)
3
(1, 1, 2), (2, 1, 1), (1, 2, 1)

(1, 1, 1)

86
The existence of degeneracy is a consequence of the symmetry of the potential
Special case: a < b < c
The ground level occurs when n x = n y = n z = 1 as before and the first excited level occurs when
n x = 1, n y = 1 and n z = 2 because, c > b and c > a.
The energy of the 1st excited level, E
=
112

2 2 1

1
4
2 + 2 + 2
2m a
b
c

, and no degeneracy exists

in the level.
Ex: When one of the dimensions of the box (say c) is zero, the rectangular potential box reduces to a
potential rectangle (in 2-d). Repeat the above derivation and look for degeneracies when a = b.

(11) Harmonic Oscillator (3-d)

Consider a particle of mass m subjected to harmonic motion in 3-dimensional space
Anisotropic case: i.e. the spring constant k has 3 different values along x, y, z directions. (k x k y
k z ). Following the same procedure given in the potential box problem, it can be shown that
En n nz = En + En + Enz =
x y
x
y

=
kx

m
=
x2 , k y

( nx + 12 ) x + ( ny + 12 ) y + ( nz + 12 ) z , where

=
m y2 , k z

m z2 .

nx n y nz ( x, y, z ) = nx ( x) n y ( y ) nz ( z ) , where
12

2 2
x
12
nx ( x ) =
e x x 2 H nx ( x x ) , with x = ( m x ) and
2 nx n !
x

n x , n y , n z = 0, 1, 2, . n y ( y ) and nz ( z ) take the same form.

Isotropic case: k x = k y = k z = k = m2

Enx n y nz =

( nx + ny + nz + 32 ) = ( n + 32 ) ,

where n = 0, 1, 2, ..

Ex: In this case, find the degeneracy in the five lowest energy levels.

87

Tutorial 3

Conservation of Probability, Probability Current Density

1. In obtaining the continuity equation we have assumed that the potential V ( r , t ) is a real quantity.

Prove
that
if
is
complex
the
continuity
equation
becomes
V (r,t)

2

P( r , t ) + . j ( r , t ) = [Im V ( r , t )]P( r , t ) so that the addition of an imaginary part of the

t
potential describes the presence of sources if Im V > 0 or sinks (absorbers) if Im V < 0.
Superposition Principle, Normalisation, Expectation values and Uncertainties
2. One thousand neutrons are in a one-dimensional box with walls at x = 0, x = a. At t = 0, the state
of each particle is ( x, 0) = Ax ( x a) .
(a) Normalize and find the value of the constant A.
(b) How many particles are in the interval (0, a/2) at t = 0 ?
(c) How many particles have energy E 5 at t = 0 ?
(d) What is E at t = 0 ?
3. Let E n denote the bound-state energy eigenvalues of a one-dimensional system and let n (x)
denote the corresponding energy eigenfunctions which satisfy the orthonormality condition. Let
(x, t) be the wave function of the system, normalised to unity, and suppose that at t = 0 it is
given by ( x, t = 0) = 2 1 ( x) + 3 2 ( x) . Write down the wave function (x, t) at time
5
5
t. (a) Find the probability that at time t a measurement of the energy of the system gives the value
E 2 , (b) Does x vary with time ? Does p x vary with time ? Does E = H vary with time ?
4. Consider the function ( ) of the angular variable , restricted to the interval . If the
d
wave function satisfy the condition () = (), show that the operator L =
has a real
i d
expectation value.
5. Consider a particle whose normalised wave function is (x) = 2xex, x > 0 and (x) = 0, x <
0, where is a constant. (a) For what value of x does P(x) = (x)2 peak ? (b) Calculate x and
x2, (c) What is the probability that the particle is found between x = 0 and x = 1/ ?, (d)
Calculate p and p2, (e) Calculate x and p and show that the uncertainty principle is satisfied
for the particle.
6. The wave function (x) of a particle in the potential V(x) = for x < 0 and V(x) = Cx for x > 0 are
given by (x) = 0 for x < 0 and (x) = Ax exp(bx) for x > 0, where A is a constant. (a) Sketch
the potential distribution, (b) Use the normalisation condition to determine the value of A, (c)
Find the expectation value of the total energy of the particle, (d) Find the value of b which gives
rise to the ground state energy of the particle.

Tutorial 4

Schrdinger Equation and its applications

7. The wave function of a particle of mass m which moves in one dimension is ( x, t ) =
A ei(k x t ) , where
A, k, and are constants. Determine the potential V(x) in which the particle moves, in terms of m, , k
and .
8. Consider an electron of energy E incident from right on the potential step defined by V(x) = 0 for x < 0
and V(x) = V 0 for x > 0. (a) Find the probability current densities in both regions and obtain expressions
for reflection and transmission coefficients, (b) Prove that the reflection and transmission coefficients are

88
the same as when the particle is incident on the potential from the left, (c) A uniform beam of electrons is
incident normally on a metal. On the assumption that outside the metal the electrons have a kinetic energy
of 1 eV, and that inside it their potential energy is 1 eV less than that of outside, calculate the fraction of
electrons reflected from the metal surface.
9. A particle of total energy 9V 0 is incident from the x-axis on a potential given by V(x) = 8V 0 for x < 0, V(x)
= 0 for 0 < x < a and V(x) = 5V 0 for x > a. Find the probability that the particle will be transmitted on
through to the positive side of the x-axis, x > a.
10. Consider a particle incident from the left on a potential step which is defined as V(x) = V 1 for x < 0 and V(x)
= V 2 for x > 0 with V 1 < V 2 . Find the solution of the Schrdinger equation for the following cases: (i) V 1 <
E < V 2 (ii) E > V 2 .
11. Set up the Schrdinger equation for a two-dimensional harmonic oscillator in the Cartesian co-ordinates
and obtain the energy eigenvalues and the eigenfunctions.
12. Estimate the zero-point energy of an electron confined inside a region of size 1014 m, which is the order of
magnitude of nuclear dimensions. Compare this energy with both the gravitational potential energy and
the Coulomb potential energy of an electron and a proton separated by the same distance. On the basis of
this comparison, discuss the possibility that an electron can exist within a nucleus. Calculate the zero-point
energy of a neutron which is confined within a nucleus.
13. Normalise the wave functions for a particle in a box showing that the normalisation constant N = (8/abc)1/2
= (8/V)1/2, where V is the volume of the box. Obtain an expression for the energy of the particle. Now
consider a particle in a cubical potential box of side a that is very large. Find the number of quantum states
(a) with energy between E and E + dE (b) with momentum between p and p + dp. Repeat your work in
parts (a) and (b) for a particle in a large two-dimensional potential box with equal sides.
14. The ground state wave function of a particle of mass m subjected to a linear harmonic oscillatory motion in
the x-direction with a force constant k, is given by 0 (x) = Nexp(2x2), where = (mk/2)1/4 and k = m2
with being the angular frequency of the corresponding classical oscillator. (a) Evaluate N so that 0 (x) is
normalised to unity (b) Evaluate x2, V, T and p2 for the oscillator in the ground state, where V and T
are the potential and kinetic energies and p is the linear momentum (c) Evaluate the uncertainty product
x.p for the oscillator in the ground state, where x = [x2 x2]1/2 and p = [p2 p2]1/2 (d)
Determine the position of the classical turning points for the oscillator in the ground state (e) Compute the
probability that the particle is found in the classically forbidden region. (f) Obtain expressions for the
probability density of the linear harmonic oscillator (quantum mechanical) in the ground state and that of
the corresponding classical oscillator having the same energy. Then sketch roughly the variation of the
quantum mechanical and classical mechanical probability densities as a function of position.
15. Find the eigenenergies and eigenfunctions for a particle moving under the potential

m 2 x 2 2
V ( x) =

x>0
.
x0

16. A particle in an infinitely deep square potential well is found to be 70% of the time in its ground state
and the remainder in its first excited state. Write down the wave function of this particle. Show that
this is normalised and calculate the expected result for the measurements (a) position, (b) momentum
and (c) energy.

17. Show that, (a) is a Hermitian operator, (b) anti-commutes with x and p x . (c) commutes with

p x 2, V(x) and H, (d) the eigenvalues of are +1 and 1 corresponding respectively to an even
eigenstate ( e (x) say) and an odd eigenstate ( o (x) say), (e) e (x) and o (x) are orthogonal to each
other, in accordance with the fact that they belong to different eigenvalues of .

83

Separation of the Schrodinger Equation in Spherical Polar Co-ordinates

Consider the motion of a particle of mass m in a central (radial) potential V(r) (i.e. V(r) depends

only on r = r ). Since V(r) is then spherically symmetric, it is convenient to use spherical polar
co-ordinates in this problem.

z
The Cartesian co-ordinates (x, y, z) of the point P and the
spherical polar co-ordinates (r, , ) are related by

x = r sin cos , y = r sin sin , z = r cos ,

where 0 r , 0 , 0 2 .

In spherical polar co-ordinates (r , , ),

=
2

1 2
1
1


2
r
sin

+
+

r 2 r r
r 2 sin
r 2 sin 2 2

d r d3 r =

r 2 d r sin d d =

Hamiltonian of the particle,

H
where

2 2
+ V (r ) =
2m

r 2 d r d, where d = sin d d

L2
2 1 2
r

2
+ V (r ) ,

2
2
2m r r r
r

1

2
1
=
2
+

sin

sin 2 2
sin

L2

TISE for the particle,

2 1 2

L2

(r ) (r ) =

+
r
V
E (r )

2
2
r
2m r r r

Rearranging terms, assuming a solution of the form (r ) (r , , ) =

R(r )Y ( , ) and
separating variables
2 m r2
1 2
1

+
=
=
(constant)
r
R
(
r
)
E V (r )
L2Y ( , )

2
2
R(r ) r r

Y ( , )

1 2
2m

r
R(r ) + 2 E V (r ) 2 R(r ) =
0 (1)
2 r
r
r
r

Radial Equation, to be

solved for R(r)

Angular Equation, to be
L Y ( , ) = Y ( , ) (2)
solved for Y ( , )
Let Y ( , ) =( ) ( ) , substitute in the above equation with the definition of L2 and separate
variables.
2

84

sin
( )

( ) + sin 2
sin

1 2 ( )
( ) 2

m2
1

sin
(
)

sin
sin 2

d 2 ( )

=m 2 (constant)

0 . (3)
( ) =

+ m 2 ( ) =
0 (4)

Equation (4) has a particular solution,

( ) =
ei m
Using the requirement that eigenfunctions be single-valued,
(since and + 2 are the same angle)
( ) = ( + 2 )
When = 0,

=
1
cos 2 m + i sin 2 m
(0) = (2 )

m =

0, 1, 2, 3, .......... or m =

0, 1, 2, 3, ........

Normalization of ( ) requires that, when ( ) =

C ei m ,
2

( ) d

C = 1
=
1

=
m ( )

ei m ,

0 2

In Equation (3), substitute w = cos with 1 w 1

d
m2

2 d
1
w
P
(
w
)

2
P ( w)
dw
dw
1
w

0,

where ( ) P( w)

Since the wave function must be finite everywhere, P( w) and ( ) must be finite everywhere.
All possible solutions those for which P( w) is finite everywhere exist, only if
(i)
(ii)

l (l + 1), where l = 0, 1, 2, 3, ..............

m l (i.e. l m l and for a given value of l, there should be (2l + 1) values of m

such that l , l + 1, l + 2, ..... , 0, ...., ......, l 2, l 1, l .)

The angular part Y ( , ) (normalized) of the wave function (r , , ) can be written as

=
Yl m ( , )

Cl m Pl
Cl m

( w) m ( ) - known as Spherical Harmonics

( P(w) P

(2l + 1)(l m)!

(1) m
=

2(l + m)!

(2l + 1)(l m)!

(1) m

2
4 (l + m)!
1

( w)

(2l + 1)(l m)! 2 m

Yl ( , ) =
(1)
Pl (cos ) ei m , m 0

4 (l + m)!
m

( Note that,

Yl m ( , ) Yl m ( , )

In Dirac notation, the spherical harmonics,

Yl m ( , )

l m

Yl m* ( , )

l m

Spherical harmonics satisfy the orthonormality relation

m
m
=
Yl ( , ) Yl ( , ) d

=
(Yl ( , ) ) Yl ' ( , ) d sin d
0 0

* m'

l l m m

85
l m l m

In Dirac notation, the orthonormality condition,

= l l m m

For spherical harmonics yielded by a given (fixed) value of l with

m = l , l + 1, l + 2, ........., 1 , 0, 1, ........, l 2, l 1, l , the orthonormality condition
l m l m = m m .
reduces to
The low-order spherical harmonics
1

Y00 ( , )

l = 0 m = 0

3
sin e i ,
4

1 Y11 ( , )
l =
1 m =

..

Y10 ( , )

l = 1 m = 0

l =
2 m =
0 Y20 ( , )

3
cos
4

5
3cos 2 1
16

Some Important Properties of Yl m s

(1)

Yl m s form a complete set in the variables and , i. e. any angular function F ( , ) can
be expanded in terms of them.
F ( , ) =

l = 0 m = l

(2)

(3)

(Yl

al m
al m Yl m=
( , )

( , ) F ( , ) d

L2 Yl m ( , =
)

(from equation (2))

l (l + 1) 2Yl m ( , )
m
2
i.e., Yl s are eigenfunctions of L with the eigenvalue l (l + 1) 2 .

Behavior of Yl m s under the parity operation r r

( i.e. (r ) = ( r ) ) .
i.e. r r ,
,
+
z

Yl m ( , =
)

Pl

)
Yl m ( , + =

[cos( )] =
Pl

m ( + ) =
( 1)

Yl m ( , ) =

(1)

Pl

[cos( )] m ( + )

[ cos ] =
(1)

l m

Pl

(c os )

m ( )

l m

Pl

(c os ) (1)

Yl m ( , ) =
(1)l Yl m ( , )

m ( )

i.e. Yl m has the parity of l (even for even l and odd

for odd l.)

86

Physical properties of L2

t
pt

pr

Consider a particle of mass m, having linear

momentum p and position vector r with respect to

origin O. Then, the angular momentum of the

particle with respect to O is defined as L= r p .

( L is perpendicular to the plane containing

r and p . =
L
L
r p sin , where is the
=

angle between r and p )

Taking r as a unit vector along r and t as a unit vector in the plane of r and p and perpendicular

to r ,
=
p2
pr2 + pt2
=
p
pr r + pt t

Since p = i

As shown before,
=
2
p r2

p 2 = 2 2 = p r2 + p t2
1 2
L2
2 2
L2
2 2

r
+

r 2 r r
2 r 2
r 2 r r
r2
2 2
L2

L2 = r 2 p t2
+ p t2 =
2
r
+

2
r r r
r

r t is a unit vector along the direction of the orbital angular momentum. Therefore, we
identify L2 as the operator corresponding to the square of the orbital angular momentum.
In all isolated systems (with no external torques), the total angular momentum is conserved. In
classical mechanics, angular momentum is an ordinary vector. But, in quantum mechanics, it is a
vector operator and its three components do not commute with each other.

L = ( Lx , Ly , Lz ) ,
L= =
L
r p sin

The cartesian components of L are

( y pz z p y )

=
Lx

=
Ly

( z px x pz )

In q.m., the corresponding operators are

=
L x
y p z z p y
=
L y
( z p x x p z )

=
i y
z
y
z

=
Lz

=
Lz

( x p y y px )

( x p y y p x )

=
i z
x
z
x

=
i x
y
x
y

The above three relationships are represented by the vector operator L = i r

It can be verified that L is Hermitian.

Consider the commutation relation L x , L y

))

87

[ y p z ,

= y p z z p y , ( z p x x p z ) =

z p x ] [ y p z , x p z ] z p y , z p x + z p y , x p z

To evaluate each commutator individually, consider [ y p z , z p x ]

=
[ z, y p z ] p x z [ p x , y p z ]
[ y p z , z ] p x + z [ y p z , p x ] =

=
[ z, y ] p z p x y [ z, p z ] p x z [ p x , y ] p z z y [ p x , p z ]
= i y p x

Similarly, it can be shown that

[ y p z , x p z ] = 0 ,

L x=
, Ly

i x p y y p x

z p y , z p x = 0 ,

z p y , x p z = i x p y
L x , L y = i L z

L y , L z = i L x
L z , L x = i L y

Operators representing any two components of the orbital angular momentum do not
commute. i.e. they are not simultaneously measurable with absolute precision.

The above three relationships are equivalent
=
to L L
i L,
Note: L L 0

Similarly, it can be shown that

Since L2 = L2x + L2y + L2z

(Note: L 2 L 2 L

L2 , L x =

L2x + L2y + L2z , L x = L2y , L x + L2z , L x = 0

(prove this)

L2 , L z = 0
Similarly, it can be shown that L2 , L y = 0 ,

2
The above three relationships are equivalent to L , L = 0

Simultaneous eigenfunctions of L 2 and one of L s components can be found. i.e. both the
magnitude and one component of angular momentum can be measured simultaneously with
absolute precision.
In spherical polar co-ordinates, it can be shown that,

L x =
i sin
cot cos
,

L y =
i cos
cot sin
,

L z = i

1

2
1

sin
+

sin 2 2
sin
Note that, L x , L y , L z and L2 are purely angular operators. (i.e. independent of r)
L2

L2 , f (r )

=
=
0
Lz , f (r )

1 i m
1 i m
Note that,
i
=
L z m ( ) =
m
m m ( )
e
e
=

2
2

m is an eigenvalue of Lz with eigenfunction m ( ) , where m = 0, 1, 2, 3, ........

L x , f (r )
=

L y , f (r )
=

Therefore, a measurement of the z-component of the orbital angular momentum can yield the
values 0, 1, 2, 3, ........ Since the z-axis can be chosen arbitrarily, the component of the
orbital angular momentum on any axis is quantized.

88
L z m ( ) =

m m ( )

L z m ( ) ( ) =

L z Ylm ( , ) =
m Ylm ( , )

m m ( ) ( )

The eigenvalues and eigenfunctions of L 2 and Lz

Since L2 , Lz = 0 , we can look for simultaneous eigenfunctions of L 2 and L z . We see that

m
Y l ( , ) are simultaneous eigenfunctions of L 2 and L , because
z

m
L2 Yl l ( , =
)

m
m
L z Yl l ( , ) = ml Yl l ( , )

l (l + 1) 2Yl l ( , )

l = 0, 1, 2, 3, .............. is called the orbital angular momentum quantum number.

l ml l and ml = 0, 1, 2, 3, ........ is called the orbital magnetic quantum number.

Note: In order to show the connection to l, we have replaced m by ml .

We designate the orbital angular momentum states corresponding to l = 0, 1, 2, 3, .............. by

the symbols s, p, d, f, . (designation of the subshell system of atoms)
l
Designation

sharp

principal

diffuse

fundamental

[When there is more than one particle, we have L = 0, 1, 2, 3, .............. as the total orbital
angular momentum quantum number and S, P, D, F, . are used to designate their states.]
The angular part of the wave function Yl m l ( , ) , is the same for all spherically symmetric
(central) potentials. The actual shape of the potential, V(r), affects only the radial part of the wave
function, R(r), which is determined by the radial equation
1 2
l (l + 1)
2m

r
R
r
+
E V (r )
R(r ) =
(
)
0 (1)

2 r
2
r
r 2
r

By substituting u (r ) = r R (r ) , Equation (1) can be simplified into the modified radial equation

2 d 2 u (r )
l (l + 1) 2
+ V (r ) +
E u (r ) .(5)
u (r ) =
2
2m d r 2
2
mr

It is identical to the one-dimensional TISE for a particle of mass m and total energy E moving in a

potential (effective), Veff=

(r )
term.

V (r ) +

l (l + 1) 2
2m r2

. The term added to V(r) is called the centrifugal

89

The Hydrogenic Atoms

We consider the hydrogenic atom to consist of a heavy motionless nucleus (kept at the origin) of
charge +Ze together with a much lighter electron of mass me and charge e that circles around it,
held in orbit by the mutual attraction of opposite charges. eg: H(Z = 1), He+(Z = 2), Li++(Z = 3),
Be3+(Z = 4),
Z e2
( Ze)(e)
From Coulombs law, the potential energy (in SI units)
is V (r )
.
=
=
(4 0 )r
(4 0 ) r
Z e2
p 2
2 2

The Hamiltonian,
=
+ V (r ) =
+
2me
2me
(4 0 ) r
TISE for the electron reads,
Z e 2
L2

2 1 2
E (r )

(r ) =
2
r
2 2 +
(4 0 ) r
r
2me r r r
H

Since the potential is central, the angular part of (r ) are spherical harmonics. Also, the radial
equation can be shown to take the form of the modified radial equation (with u (r ) = r R (r ) ).

Z e2
2 d 2 u (r )
l (l + 1) 2
+
+
E u (r )
u (r ) =
2 me d r 2
2 me r 2
(4 0 ) r

(similar to equn (5))

Solutions to the above equation can be obtained for

(i) continuum states (with E > 0), describing electron-proton scattering
(ii) discrete bound states (with E < 0), representing the hydrogenic atom
Here we confine our attention to bound states only. It can be shown that, the physically acceptable
solutions to this equation are obtained, when
m Z e2
E = e2
2 4 0

where

1
2
n
n = 1, 2, 3, .............. and n is called the principal quantum number.

Note: For an arbitrary value of n, there are n number of possible values of l , as given by
=
l

0, 1, 2, .............., n 1 .

(recall that, l = 0, 1, 2, 3, .............. )

Energy Levels
The allowed bound state energy eigenvalues are given by
2

m Z e2 1
E1
e2
En =
, n =
1, 2, 3, ..............
2 =
n2
2 4 0 n

This is the famous Bohr formula and Bohr obtained it in 1913 by using a mixture of classical
physics and premature quantum theory. The Schrodinger equation did not come until 1924.
The energy values can also be given in the form

90
2
e2
Z2
1
2 (Z )
,
En =
m
c

e
(4 0 ) a0 2 n 2
2
n2

=
a0
where the Bohr radius,

(4 0 ) 2
=
me e2

The radii of Bohr orbits are

given by an
=

0.529 1010 m . ( = radius of the 1st Bohr orbit of H)

4 0 2 n2
=
2

me e Z

a0 n 2
Z

As n takes on values 1, 2, 3, ............., , bound state energy spectrum of hydrogenic atoms

2

m Z e2
contains an infinite number of discrete levels from E1 = e2
to zero. For atomic
2 4 0
hydrogen (Z = 1), E1 = 13.6 eV . This negativeness in bound state energies provides stability to
the atom.

Spatial wave functions of different states in hydrogenic atoms are labeled by three quantum

nl ml (r ) = Rn l (r ) Yl ml ( , ) .
numbers n, l and ml as
However, En depends only on n and is independent of (i.e. degenerate with respect to) l and ml .
Next, we can find the number of different states of this type possible for a bound level of
energy En , which is the degeneracy of that level.
For each value of n, l may
take on values, l
=

0, 1, 2, .............., n 1 (i.e. n number of values)

For each l value, ml may take on values in the range, ml = l , l + 1, ... 1, 0, 1, ........, l 1, l
(i.e. 2l + 1 number of values)
n 1
2n(n 1)
* The total degeneracy of the bound state energy level En = ( 2=
l + 1)
=
+ n
n2
2
l =0
The hydrogenic energy levels depend on n and are independent of l and ml . The degeneracy with respect
to ml is present for any central potential. But, the degeneracy with respect to l is a characteristic of the
Coulomb potential. (i.e. V (r ) 1 r ).

The n-fold degeneracy with respect to l is removed when the dependence of V(r) is modified to become a
non-Coulombic potential. Then, the energy of the electron becomes dependent on l and gives rise to n no. of
distinct energy
levels as En l ( l
=
0, 1, 2, .............., n 1 ). Eg: Alkali atoms
The 2l + 1 - fold degeneracy w.r.t. ml is removed when an external magnetic field is applied. Then, the
energy becomes dependent on m l.

Spectroscopically, atomic states are labeled as n l .

Ground level (n = 1)

For eg: 1s, 2s, 2p, 3s, 3p, 3d, ..

l=0

ml = 0
Total # of possible states = 1

1s state only
(Degeneracy = n2 = 1)

91
l=0

First excited level (n = 2)

ml = 0

2s state

l=1

ml = 1, 0, +1 2p 1 , 2p0 , 2p +1 states
Total # of possible states = 4
(Degeneracy = n2 = 4)

We see that the energy levels predicted by the Bohr theory and by Schrodinger theory agree with
each other. But, the Schrodinger theory is more powerful, because, the eigenfunctions it yields
enable us to calculate probability densities, expectation values of operators, transition rates, etc.

The radial eigenfunctions of bound states

It can be shown that, physically acceptable solutions to the radial equation are
Rn l (r ) = N e 2 . l L2n l++l 1 ( ) ,

where N is a normalization constant and the associated Laguerre polynomials

n l 1
2Z
[(n + l )!]2 k
k +1
with =
L2n l++l 1=
( )
(

1)

(n l 1 k )! (2 l + 1 + k )!
n a0
k =0

Normalization of Rnl (r )

na
N 0
2Z
2

e
0

2l

Rnl (r )

2
L2n l++l 1 ( )

2 2

r dr = 1

d = 1

n a 2n [ (n + l )!]
N 0
2 Z (n l 1)!
2

Normalized radial eigenfunctions for the bound states of hydrogenic atoms are given as
12

2 Z 3 (n l 1)!

Rn l (r ) =

3
n a0 2 n [(n + l )!]

e 2 . l L 2n l++l 1 ( )

Using the above expression, the first few radial eigenfunctions can be written as follows.
When n = 1

l=0 =

R10 (r )

32

2 ( Z a0 )

exp ( Z r a0 )

= 1

92
When n = 2 l = 0 and 1

R20 (r ) =

=
R21 (r )
When n = 3 l = 0, 1 and 2

32

2 ( Z 2 a0 )

1
3

(Z

32

2 a0 )

R30 (r ) = ..... ,

(1 Z r

(Z r

2 a0 ) exp ( Z r 2 a0 )

a0 ) exp ( Z r 2 a0 )

R31 (r ) = ...... ,

R31 (r ) = ......

For the first few functions, Rn l (r ) vs. r and r 2 Rn2l (r ) vs. r plots are as given below.

We can use the known expressions of Rn l (r ) and Yl ml ( , ) in nl ml (r ) = Rn l (r ) Yl ml ( , ) to

obtain the wave functions of the first few states of hydrogenic atoms as follows.
n=1

n=2

l=0

l=0

l=1

ml = 0

=
100 (r )

ml = 0

(r )
200=

ml = 0

=
210 (r )

Y00 ( , ) = 1

( Z a0 )3 2 exp ( Z r

1
2 2

1
4 2

a0 )

Y00 ( , ) = 1

( Z a0 )3 2 (1 Zr
Y10 ( , )

( Z a0 )3 2 ( Zr

2a0 ) exp ( Z r 2a0 )

3
cos
4

a0 ) exp ( Z r 2a0 ) cos

93
ml =

Y11 ( , )

3
sin exp ( i )
4

=
21 1 (r )
( Z a0 )3 2 ( Z r a0 ) exp ( Z r 2a0 ) sin exp ( i )
8

In the above work on hydrogenic atoms, it was assumed the mass of the nucleus to be infinitely
large when compared to the electron mass so that the nucleus remains fixed in space (at the origin).
This is a good approximation even for hydrogen, because mnuc 2000 me . However, for a better
agreement of the above theoretical results with accurate spectroscopic data, it requires the nuclear
mass to be taken into account as finite. In such a situation, the electron and the nucleus revolve
around their common centre of mass and it is possible to show that the electron moves around the
nucleus as though the nucleus is fixed and the mass of the electron is slightly reduced to a value
called the reduced mass of the system. The equations of motion of the electron-nucleus system are
the same as those we have considered before, if we simply substitute for me
It can be shown that,

M me .

me M
, where M is the mass of the nucleus.
me + M

As

Under this change, the more accurate expressions of energy eigenvalues and energy eigenfunctions
can be obtained by replacing me by in the relevant expressions.
Eg:

e2
Z2
Z e2 1
En =
2
=

(4 0 ) a 2 n 2
2 4 0 n 2

me
(4 0 ) 2
=
a .
0
e2
The fraction by which the energy levels of a hydrogen atom is shifted =
M

=
, a
and the modified Bohr radius

=
me

=
me + M

1,836
= 0.99945 .
1,837

The more accurate expressions of radial wave functions and energy eigenfunctions can be obtained
by replacing a0 by a in the relevant expressions.

Eg: R10 (r ) 2 Z a
=

32

exp Z r a

100 (r )
=

( Z a )

32

exp Z r a

Consider an electron in a stationary state nl ml (r , , ) .

Position Probability Density = nl ml (r , , )

= Rn l (r ) 2 Yl ml ( , )

Probability of finding the electron in the volume element dr at the point r = nl ml (r , , ) 2 d r

94
Probability of finding the electron in the shell of inner and outer radii r and r + dr

=
0=
0
2

d sin

=
0=
0

= r Rn l (r ) d r

d sin

=
0=
0

nl ml (r , , ) 2 d r =

d Yl l ( , )

d nl ml (r , , ) 2 r 2 d r

since d sin d Yl ml ( , )

0=
0
=

= r Rn l (r ) d r

= 1

= Dn l (r )d r ,
where the Radial Distribution Function,
Rn2l (r )

Dn l (r ) = r 2 Rn2l (r ) =

Dn l (r ) = r 2 Rn2l (r ) ,

Rn l (r ) = Rn2 l (r )

Electron density along a given direction

Probability of finding the electron within a unit length at a distance r
in any direction from the nucleus (i.e. within a shell of radius r and of
unit thickness).

Consider the ground state of hydrogen (Z = 1), n = 1, l = 0, m l = 0.

1
100 (r ) =
1s (r )
(1 a0 )3 2 exp ( r a0 )

As can be seen from the plots given below, 1s (r ) and 12s (r ) are exponentially decreasing
functions of r with their maximum occurring at the origin
To make a comparison of quantum mechanical results with those of Bohr theory, we look for the
Radial Distribution Function of the ground state.
2
D1 0 (r ) = r 2 R10
(r ) ,

where
=
R1 0 (r ) 2 (1 a0 )

32

exp ( r a0 )

[Note: For states where (r ) is independent of and (eg: 1s, 2s, 3s, ..)
2

Probability distribution function = 4 r 2 .]

The maximum in D1 0 (r ) curve plotted versus r indicates that the probability of detecting the
electron is maximum at some distance. This value of r is called the most probable distance and to
find it
d

r = a0
D1 0 (r ) = 0
dr
So, Q. theory is similar to the Bohr picture of the hydrogen atom. However, there is a finite
probability of seeing the electron at other values of r between 0 and and therefore the size of the
atom is not well-defined in Q. theory.
The value r can also be calculated for the ground state of hydrogen, as follows.

*
r =
exp( 2r a0 ) r 3 d r sin d
1s (r ) r 1s (r )d r =
3
a0 0
0

d
0

3
=
a0 > m. p. d.
2

95
As we see, the mean value is found to be larger than the most probable distance. This is because of
the diffuseness incorporated by quantum theory to the electron orbit making it an electron cloud.
According to quantum theory, the electron can be found at distances from r = 0 to r = from the
nucleus with various probabilities (The maximum probability occurs at r = a ). So, their average
value is found to be equal to 1.5a . The Bohr theory predicts precisely a as the distance where
the electron can be found. However, in quantum theory, that is the distance where the electron can
be found with the maximum probability.

To obtain a reasonable estimate for the size of the atom, we find a value r(0.9) such that there is a
90% probability that the electron is at a distance r r(0.9) .
r(0.9)

=
Prob.

2
=
r R10
(r ) d r
0

0.9

2
a03

r(0.9)

r(0.9) = 2.6 a0 .
exp( 2r a0 ) r 2 d r =
0.9

For most purposes, an effective atomic radius is taken as from a0 2.5a0 ~ 108 cm = 1 .
Classically, a moving particle has a turning point when the total energy = potential energy. At this
point, the kinetic energy (hence the velocity) = 0 and the particle is expected to be reflected by the
potential barrier.
For an electron in the ground state of hydrogen atom, classical turning point occurs, when
V (r ) = E1

e2
e2
=
(4 0 )r
2(4 0 ) a0

r = 2 a0 .

As shown by D10 (r ) versus r curves, there is a finite probability of finding the electron for
r > 2a0 . i.e. the electron has access to a region which is forbidden by classical theory. This effect
of tunneling (penetration) through potential barrier is typical in q. theory results.

96
For values of r > 2a0

V > E , and in order to satisfy the condition E= T + V , the

kinetic energy T would have to be negative. This unrealistic situation can be explained by using
H. u. p. as follows.
In q.m., a particle is in a certain region means that its position measurement has been made (with
some uncertainty). According to the u. p.
uncertainty in position

uncert. in momentum

uncert. in kinetic energy

It can be shown that, when the electron is in the classically forbidden region, the uncertainty
introduced to its kin. energy is sufficiently large to compensate for the negative value required by
conservation of energy.
The energy eigenvalue equation (TISE) for a hydrogenic atom reads
E

H nl m (r ) = En nl m (r ) , where En = 21 , n = 1, 2, 3, ..........
l
l
n
2
e
Z2
Ionization potential in the nth shell, =
IP
En
=
(4 0 ) a 2 n 2
m
m
nl m (r , , ) =
Rn l (r ) Yl l ( , ) =
Rn l (r )(1)l Yl l ( , )

nl m (r , , ) =

(1)l nl m (r , , )
l

nl ml s have the parity of l.

In Diracs notation, nl m (r ) n l ml
l

Eigenfunctions nl ml (r ) form an orthonormal basis as given by

*
n l m (r ) n lm (r ) d r = n n ll ml ml or equivalently n l ml n l ml = n n ll m
l

ml

Once nl ml (r ) functions are known, the solutions to TDSE are given by (r , t ) =

n l ml (r ) e i En t .

Energy levels and spectrum of the hydrogen atom

In his model, Bohr had postulated that transitions can take place between states with any two values
of the q. no. n. This fact is justified by quantum mechanical calculations of transition probabilities.
However, these calculations also suggests that for allowed transitions, the q. no. l changes by 1 .
In addition, the q. no. ml changes by 0 or 1 . Therefore, the selection rules for the most common
spectral transitions due to the interactions between the electron and the dipole electric field of the
radiation are
n1 n2 =n arbtrary,
l1 l2 =l = 1,
ml1 ml2 =ml =0, 1 ,
where the symbols n1 , l1 , ml1 correspond to the initial state and the symbols n2 , l2 , ml2 correspond to
the final state of the transitions. The states and allowed transitions for the hydrogen spectrum for
n = 1, 2, 3, 4, are shown below.

Shown below is only the gross structure of hydrogenic atom energy levels and possible transitions
among them. Due to other interactions which exist within atoms, transitions do not occur exactly
according to the dipole selection rules.

97

Note: Whenever an integration over whole space is performed on hydrogenic wave functions, even
if they are found to be independent of and , three separate integrations over r, and
must be performed over the ranges, r = 0 to , = 0 to and = 0 to 2 with differentials,
r 2 dr , sin d and d , respectively.
m

When an integration is performed on a spherical harmonic function, Yl l ( , ) , two

separate integrations over and must be performed over the ranges, = 0 to and = 0
to 2 , with differentials sin d and d , respectively.
When an integration is performed on a Radial function, Rn l (r ) , an integration over r must
be performed over the range r = 0 to , with the differential r 2 dr .

98

Orbital angular momentum and orbital magnetic Dipole moment of the electron
Consider a hydrogen atom and assume the electron orbit as circular. Since this acts as a current
loop, there is a magnetic field in the direction perpendicular to the plane of the orbit.

e
me

I Current

At large distances from the loop, the B field produced by the current loop is similar to that

produced by a magnetic dipole placed at the centre of the orbit.

The magnetic dipole moment due to a current loop enclosing a small area dA, M = IdA

M is in a direction normal to the loop.

e
Current (magnitude) due to electron,
=
T

e
=
2 r v

ev
2 r

dA = r 2

Area of the loop,

Orbital magnetic dipole moment (magnitude) of the electron, M L =

L = me v r

Orbital angular momentum (magnitude) of the electron,

ML
L

Usually,

ev r
1

2
me v r

e
=constant
2me

ML
ML
is written =
as,
L
L

M L = gl

( M L )z

ML =

gl

e
gl
=
2me

gl

Bohr magneton, =
B

Orbital g-factor, gl = 1

B L

ev
evr
r2 =
2 r
2

Lz

gl

B L

e
=
2 me

9.27 1024 J T 1

( M L is anti-parallel to L )

99

Quantum mechanically, it can be shown that L L =

l ( l + 1) , where l = 0, 1, 2, .. is the

orbital angular momentum quantum number.

Note: This L is the average value of the magnitude of the orbital angular momentum.
Depending on the value of l, we can characterize the orbital angular momentum states of electrons
in atom as s, p, d and f sub shells (states).
Quantum mechanically, it can be shown that Lz = ml ,

L x = L y = 0.

Note: These L x , L y , and L z are the average values of the components of orbital angular momentum.
m l is the orbital magnetic quantum number.
Quantum mechanically, it can be shown that, for a given value of l, ml varies in the range
l ml l , in integer steps. For a given values of l, there are (2l +1) number of m l
values.
Possible values of m l are l, l + 1, l + 2, , 0, .... , l 2, l 1, l
For s- states,

l=0

0 ml 0

ml = 0

one value

For p- states,

l=1

1 ml 1

m l = 1, 0, 1

three values

For d- states,

l=2

2 ml 2

m l = 2, 1, 0, 1, 2

five values

For f- states,

l=3

3 ml 3

m l = 3, 2, 1, 0, 1, 2, 3 seven values

Quantum mechanically,

M
=
L

Quantum mechanically, ( M L ) z =

gl

gl B

B L
gl =

ML
=

B Lz

gl

l ( l + 1)
=

ml =

gl B l ( l + 1)

gl B ml

For a given value of l, ( M L ) z can have (2l + 1) number of discretely quantized values.
Note: These M L and ( M L ) z are average values of the respective quantities.

Vector model of orbital angular momentum

L L=

l ( l + 1) , where l = 0, 1, 2, .

Lz = ml , and for a given value of l, l ml l .

Lx = Ly = 0

The above facts suggest that the orbital angular momentum L precess about the axis of
quantization (z-axis) so that its (2l + 1) # of projections on that axis are given by Lz = ml (m l are

l, l + 1, l + 2, , 0, .... , l 2, l 1, l). L may be viewed as lying on the surface of a

100

cone with altitude of ml and z-axis as the axis of symmetry. All the orientations of L on the
surface of this cone are equally probable.
Eg: When l = 1
z

Axis of quantization

ML

ML

2,

ML
l = 1, L =

L z = , 0, +

cos = 1

Since q.m suggests the vector model of orbital angular momentum, it also suggests the vector
model of orbital magnetic moment.

( M L ) z can have (2l + 1) # of discretely quantized values.

However, classically L (hence M L ) can have any # of orientations with respect to the z-axis. i.e.
M L ( M L )z M L
An atom possesses magnetic dipole moment due to the

atom is in an external magnetic field of strength B ,

V = ML B

The net force acting on the atom,

F = V = +

Fx

B
,
M
Fy
=
L
x

orbital motion of the electron. When an

the potential energy of the interaction

(M L B)

= ML B

B
B
,
,
ML
Fz M L
=
y
z

If B is uniform, then F x = F y = F z = 0.

Stern and Gerlach Experiment (1922)

This experiment was carried out to measure the magnetic dipole moments of atoms by detecting the
deflection of an atomic beam by an inhomogeneous magnetic field.

101
Magnetic
poles

z
y

Inhomogeneous
magnetic field

B field lines
Beam of silver
atoms

Collecting plate
A collimated beam of Ag atoms entered the inhomogeneous magnetic field between the magnetic
poles and was detected after falling on a cooled collecting plate. (The whole setup was under
vacuum) Due to the geometry of the magnets, the force acting on the atoms was mainly in the zdirection.
Fz = ( M L ) z

B
z

Along the x-axis,

B
z

- field gradient

remains constant.

Fz ( M L ) z

With no
magnetic field

With magnetic field on

(Classically expected)

With magnetic field on

(Observed)

Since the field gradient is a maximum at the center, F z is maximum at the center and the deflection
should be maximum. If the magnetic moments of the atoms are randomly oriented as expected
classically, every value of ( M L ) z such that M L ( M L ) z M L would occur and the deflected
beam would be spread into a continuous band (Fig. 2). Quantum mechanically only discretely

102
quantized values of ( M L ) z are possible ( ( M L ) z = gl B ml ) and hence the deflected beam would
be split into several discrete components. (According to Fz = ( M L ) z

B
z

). What Stern &

Gerlach observed was two distinct lines (Fig. 3). This is called the space quantization of the
components of the magnetic dipole moment along the direction defined by the magnetic field (i.e.
z-direction)
We know that,
l is an integer

# of possible m l values for a given l = (2l + 1 ) is an odd integer.

For any value of l, one of the m l values is zero.

There

should

be

an

undeflected

component of the Ag atomic beam (because m l = 0 result in a zero force)

Consider Ag atom
Ag (Z = 47): 1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p6 5s1 4d10
The net magnetic moment of an Ag atom is determined by the single 5s electron (all the other 46
electrons in completely filled sub shells contribute to nothing.)
For an s electron

l=0

ml = 0

( M L )z

=0

Fz = 0

No deflection in the Ag beam is possible but, Stern & Gerlach observed two deflections!
An explanation came from Goudsmit and Uhlenbeck in 1925. i.e., in addition to the magnetic

moment produced by the orbital motion, electron may possess an intrinsic magnetic moment, M s ,

where the component of M s in a given direction (z-axis) can take only two values. It can be

postulated that M s is due to an intrinsic angular momentum S of the electron.

( )

Spin angular momentum of the electron

Similar to the relationship of M L with L , we have

B S
,
g s Spin g-factor (spin gyromagnetic ratio),
M S = gs

Spin magnetic moment of the electron.

Ms

gs 2

Unlike the orbital angular momentum the spin angular momentum does not correspond to any

physical motion. (i.e., it is not possible to write a relationship equivalent to L= r p for S )

Quantum mechanically, S and S z are defined to have average values

103

s ( s + 1) ,

S=

S z = ms

For a given value of s, s ms s

(2s + 1) # of ms values (s, s + 1, s + 2, . , s 2, s 1, s) are possible.

s Spin angular momentum quantum number

ms Spin magnetic quantum number

Average values of S x = 0 and S y = 0 .

For electrons, s =

1
2

S =

12 ms

1
2

and
=
Sz

1
1
ms =
and +
2
2

and

For other subatomic particles such as protons, neutrons, s =

1
2

1.
2

They are commonly called spin-

particles or fermions.

For photons, s = 1

S =

1 ms 1

ms = 1, 0, +1

Sz =
, 0 , +

and

Quantum mechanically defined values of S , S x , S y and S z suggest the vector model of spin
angular momentum.
Eg:

s =

1
2

Axis of quantization

MS

S=

3 2

S=

3 2

MS
Since S z values are quantized

( M S )z

= gs

B S z

= gs

Spin up

Spin down

( M s ) z must also be quantized.

( )

ms = g s B ms = 2 B 12

= B

The force responsible for splitting the silver atomic beam in S & G experiment,

104
B

( M s ) z z

Fz =

Magnetic moment of the Ag atom

47
47

+
M =
M
ML
L
MS =

)i

=i 1 =i 1

s - electron

l = 0

ms =

)5s + ( M S )5s

)i

=
0 gs

ml = 0

1
2

s=

1
2

s=

1
2

B s ( s + 1)

m s = 12

ms = 12
ml = 0

p - electrons

l=1

m l = 1, 0, +1

ml = 0

m l = 1

m s = 12

ml = 1

This explains why it is possible to accommodate 2 electrons in an s-subshell and 6 electrons in a p-subshell,
etc.
Electron beams which have equal #s of Spin up and Spin down electrons are called

unpolarized

electron beams and those which have unequal # of Spin up and Spin down electrons are called
polarized electron beams.
The degree of polarization = P =

N N
N + N

N and N are the #s of spin up and spin down electrons in the beam.
For an unpolarized electron beam,
For a polarized electron beam,

N =

N N

For a perfectly polarized beam, N = 0

P0

( or N = 0 )

S G magnets are sometimes called spin filters.

P=0

P =1

The total angular momentum of a many-electron atom=

is J

Si
i

(0

P 1)

Li , and only those electrons in

i

incompletely filled subshells contribute to the above summations. Just as in the cases of orbital and spin

angular momenta, the (average) values of J and its z-component J z are given by

j ( j + 1) and m j ,

105
respectively. Also, for a given value j (which can take integer or half integer values only), m j can take (2j +
1) number of values as given by j, j + 1, j + 2, .., j + 2, j 1, j. Since the total magnetic dipole

moment M is determined by the values of J and the z-component of the dipole moment M z is determined

by the values of J z , one can expect (2j + 1) # of different orientations of M w.r.t. the z-axis (2j + 1) #
of M z values are possible.
Thus in a S-G experiment, if a beam of many-electron atoms (with some # of electrons in the unfilled
subshell) is found to produce x # of spots on the detection plate

x = 2j + 1

=
j

( x 1)

2.

The magnitude (average value) of the total angular momentum of the atom =

j ( j + 1)

Tutorial 5
TISE in Spherical Polar Co-ordinates, Orbital Angular momentum, Hydrogenic Atoms
1.

(i) If n l m l (r ) describes the energy eigenfunction of the electron in the nth state of a hydrogen atom,
describe the quantum numbers which characterize energy eigenstates and give their limits. Sketch
energy levels and indicate possible eigenstates (using the above notation) up to the 2nd excited level.
(ii)Explain briefly why the sub states (shells) 1p, 1d, 1f, 2d, 2f, 3f, etc, can not occur in atoms.
(iii) Explain briefly why it is not possible to accommodate more than 02 electrons in a s-sub state, 06
electrons in a p-sub state, 10 electrons in a d-sub state, 14 electrons in a f-sub state, in an atom.

2. Find the energy eigenfunctions and the corresponding energy eigenvalues of a particle of mass m, that
rotates on a circle of radius R in a potential V(r), where V(R) = V 0 .

1
1 2
2
In
plane
polar
co-ordinates
(
r
,
),
r

r r r
r 2 2

3.

Write down the time-independent Schrdinger equation for a particle of mass m that is constrained to
move on the surface of a sphere of radius R. Then, for the case in which the particles potential energy
is zero, find the energy eigenvalues and energy eigenfunctions and check for any degeneracies.

r , , ), 2
In spherical polar co-ordinates (=

1 2
1
1


2
sin
r

+
+

r 2 sin 2 2
r 2 r r
r 2 sin

4. At a given instant of time, a quantum system is in the normalized orbital angular momentum state
( , ) = N sin sin , where N is the normalization constant.
(i) Determine the constant N.
(ii) What possible values of Lz will be found by measurement and with what probability will these
values be occurred ?

(iii) What is L2

for this state ?

(iv) What is Lz

for this state ?

Some useful spherical harmonics are

Y1 1 ( , ) =

3
sin e i .
8

106
5. Consider an electron in a hydrogen atom whose wave function at t = 0 is the following superposition of

energy eigenfunctions n =
(r , t
l ml ( r ) :
(i)
(ii)

0) =

2 10 0 (r ) 3 2 0 0 (r ) + 32 2 (r )

14

Is the wave function an eigenfunction of the parity operator ?

What is the probability of finding the system in the ground state (100) ? In the state (200) ? In the
state (322) ? In another energy eigenstate ?

(iii) What is the expectation value of the energy (in terms of En ): of the operator L2 ; of the operator

Lz ?

6. Consider a hydrogen-like atom with atomic number Z, containing an electron in the ground state (1s).
The wave function of this electron is =
N exp Z r a , where N is the normalization
1s ( r )

constant, r is the radial co-ordinate and a is the modified Bohr radius.

(i)
Determine the constant N.
(ii)
Determine the average value of the potential energy of the electron.
2

and 4 r 2 1s

(iii)

What is meant by the quantities 1s

(iv)
(v)

Evaluate the average value of the distance to the electron from the origin.
Evaluate the distance from the origin at which the probability of finding the electron is a
maximum.
Comment on your results for parts (iv) and (v).
Determine the classically forbidden region for the electron in the ground state of a hydrogen
atom, if its bound-state energy eigenvalue is 13.6 eV.
What is the probability of finding the ground state electron in this region ?

(vi)
(vii)
(viii)

It is given
that, I
=

n a y

y e dy
=
0

n!
a n +1

, where Real(a ) > 0 and n is a positive integer.

7. A system is found to be in an orbital angular momentum state which is a mixture of orthonormal basis

1 1 + 1 0 + 1 1 , where , and
states corresponding to l = 1, as given by=
are real numbers.
(i)
What is the condition that needs to be satisfied by , and , for the normalization of ?
(ii)

Find the expectation values of the operators L z and L2 for the state of the system.

Electron's Spin Angular Momentum, Spin-Orbit Interaction

8. With regard to a Stern-Gerlach experiment, in each of the following cases, illustrate the recorded
configuration of the atomic beam that would be seen on the on the detecting plate giving reasons. (a) If the
magnetic field was turned off (b) If the magnetic field was homogeneous (c) If the magnetic field was
inhomogeneous and the space quantization did not exist (d) If the magnetic field was inhomogeneous and
the space quantization did exist
9. A beam of hydrogen atoms, emitted from an oven running at a temperature 400 K, is sent through a SternGerlach magnet of length 1 m. The atoms experience a magnetic field with a gradient of 10 T/m. Calculate
the transverse deflection of a typical atom in each component of the beam, due to the force exerted on its
spin magnetic dipole moment, at the point where the beam leaves the magnet.
10. Consider a beam of particles of mass M and spin , propagating in the +x-direction. The beam has a
cross section d. It interacts with an Stern-Gerlach apparatus whose field is in the z-direction.
Employing relevant uncertainty relations, show that the smallest uncertainty in the normal displacement
(z) grows large with decreasing mass.
Prepared by:
Dr. WMKP Wijayaratna
Department of Physics

Revised in September 2007

107
University of Colombo,
Colombo 03.