6

Dirac notation

A frequently used notation is the Dirac notation or bra-ket notation and is

given by
!

m
n d "m |n # "m|n#
(293)

where "m | is called the bra and |n # is called the ket and was introduced
by Dirac, hence the name. Similar the expectation value of an operator A is
!

m
An d "m | A |n # "m| A |n#
(294)
Lets consider the definition of a Hermitian operator
"!
#
!
!

m An d = n (Am ) d =
n Am d

(295)

therefore, this reads in Dirac notation

"m | A |n # = "n | A |m #

(296)

Simultaneous eigenvalues

are two operators that commute then it is possible to that there

If A and B

exits a complete set of functions that are eigenfunctions of both A and B.

We have already seen from the algebraic solution to the harmonic oscillator
the usefulness of commutators. We have the following commutator identities
[A, B] = [B, A]
[A, An ] = 0
[kA, B] = [A, kB] = k[A, B]
[A, B + C] = [A, B] + [A, C]
[A + B, C] = [A, C] + [B, C]
[A, BC] = [A, B]C + B[A, C]
[AB, C] = [A, C]B + A[B, C]

(297)
(298)
(299)
(300)
(301)
(302)
(303)

Lets use these identities for the position and momentum operators:
[x, p] = [x, i!

] = i![x,
] = i![ , x] = i!
x
x
x
39

(304)

and for the momentum squared

[x, p2 ] = [x, p]p + p[x, p] = i!(i!

) i! i! = 2!2
x
x
x

(305)

and for the commutator between the position and Hamiltonian

[x, H] = [x, T ] + [x, V ] = [x, T ] = [x, (1/2m)(p2x + p2y + p2z )]

(306)

i!
!2
= px
m x
m

(307)

= (1/2m)[x, p2x ] =

We have already discussed that when two operators do not commute that
it is not possible to have a simultaneous eigenfunction of both operators
and it is not possible to measure them with definite values in accordance
with the uncertainty principle. When measuring a property that is not an
eigenfunction of the operator we can get various different outcome in the
measurements. The get a measure for the spread in the values we consider
the variance of an operator defined as
!
2
< A >)2 d
(A) =< (A < A >)2 >= (A
(308)
One can show that using Schwarz inequality that the product of the standard
deviation of two operators are given by
$!
$
$
1 $$

(309)
AB ! $ [A, B]d $$
2

Thus, if the two operators commute the integral is zero. For the momentum
and position operators we get
$!
$
$!
$
$!
$
$ 1$
$ 1
$
$
1 $$

xpx ! $ [x, p]d $$ = $$ i!d $$ = ! |i| $$ d $$ = i!

2
2
2
(310)
which is Heisenberg uncertainty principle.
Another important uncertainty relation is between the time and energy
1
Et ! !,
2

(311)

but it was not obvious what t is, because the time at which the particle has
a given state is not an operator belonging to the particle, it is a parameter
40

describing the evolution of the system. A state which only exists for a short
time cannot have a definite energy. In order to have a definite energy, the
frequency of the state needs to be accurately defined, and this requires the
state to hang around for many cycles, the reciprocal of the required accuracy.
For example, in spectroscopy, excited states have a finite lifetime. By the
time-energy uncertainty principle, they do not have a definite energy, and
each time they decay the energy they release is slightly different. The average
energy of the outgoing photon has a peak at the theoretical energy of the
state, but the distribution has a finite width called the natural linewidth.
Fast-decaying states have a broad linewidth, while slow decaying states have
a narrow linewidth. The relationship is
! = 1/t

7.1

(312)

Angular momentum of a one-particle system

In classical mechanics a particle of mass m moving in a direction given by

the vector r
r = ix + jy + kz
(313)
and with a speed

dr
dx
dy
dz
=i +j +k
dt
dt
dt
dt
The particle momentum is then
v=

p = mv

(314)

(315)

and the particles angular momentum is

L= rp
where L is defined as

$
$ i j k
$
L = $$ x y z
$ px py pz

(316)
$
$
$
$
$
$

(317)

and we get the three components of the angular momentum as

Lx = ypz zp y
Ly = zpx xpz
Lz = xpy ypx
41

(318)
(319)
(320)

Having established the classical expressions for the angular momentum we

can straightforwardly write down the corresponding quantum mechanical
operators
"
#

Lx = i! y
z
(321)
z
y
"
#

Ly = i! z
x
(322)
x
z
"
#

y
(323)
Lz = i! x
y
x
we will refer to these orbitals as orbital angular momentum. The square of
the orbital momentum is given by
L2 = |L|2 = L L = L2x + L2y + L2z

(324)

We are now interested in establishing the commutator relations for the orbital
angular momentum operators. Operating on some function f (x, y, z) with
Ly we get
f
f
x )
(325)
Ly f (x, y, z) = i!(z
x
z
continuing to operate with Lx gives
Lx Ly f = !2 (y

f
2f
2f
2f
2f
+ yz
yx 2 z 2
+ zx
)
x
zx
z
yx
yz

Similarly we get
Lx f (x, y, z) = i!(y

f
f
z )
z
y

(326)

(327)

and
Ly Lx f = !2 (zy

2f
2f
2f
f
2f
z2
xy 2 + x
+ xz
)
xz
xy
z
y
zy

(328)

Subtracting these two equations gives

Lx Ly f Ly Lx f = !2 (y
where we have used that

f
f
x ) = i!Lz
x
y

2
2
=
zx
xz
42

(329)

(330)

thus, we get
[Lx , Ly ] = i!Lz

(331)

We can notice that there is a cyclic permutations symmetry of x, y, z in the

operators. Therefore, the two other commutators are
[Lz , Lx ] = i!Ly

(332)

[Ly , Lz ] = i!Lx

(333)

and
Thus, the components of the orbital angular momentum operators do not
compute. What about the length of the angular momentum ? We get
[L2 , Lx ] = [L2x + L2y + L2z , Lx ]
=

[L2x , Lx ] + [L2y , Lx ]
[L2y , Lx ] + [L2z , Lx ]

(334)
+

[L2z , Lx ]

(335)

=
(336)
= [Ly , Lx ]Ly + Ly [Ly , Lx ] + [Lx , Lx ]Lz + Lz [Lz , Lx ] (337)
= i!Lz Ly i!Ly Lz + i!Ly Lz + i!Lz Ly = 0
(338)
Therefore,
[L2 , Lx ] = 0
[L2 , Ly ] = 0
[L2 , Lz ] = 0

(339)
(340)
(341)

Therefore, we can only specify the magnitude of the orbital angular momentum and one of its components, which we usually take as the z component.

7.2

The angular operators in spherical coordinates

Using the relationship between cartesian and spherical coordinates

x = r sin() cos()
y = r sin() cos()
z = r cos()

43

(342)
(343)
(344)

we get obtain in spherical coordinates the angular momentum operators as

"
#

Lx = i! sin() + cot() cos()

(345)

#
"

(346)
Ly = i! cos() cot() sin()

Lz = i!
(347)

by squaring the components we get

#
" 2

2
2
2
+ cot() +
L = !
2
sin2 () 2

7.3

(348)

Orbital angular-momentum eigenfunctions and eigenvalues

We already shown that we L2 and Lz commute and we can therefore find a

function that is eigenfunction of both operators. We denote this functions
Y (, ). We are thus interested in solving but
Lz Y (, ) = bY (, )

(349)

L2 Y (, ) = cY (, )

(350)

and
where b and c are the eigenvalues. Using the Lz operator we get
!

Y (, ) = bY (, )

(351)

We can use separation of variables

Y (, ) = S()T ()

(352)

Using this we get

S()T () = bS()T ()

dT ()
= bS()T ()
i!S()
d
ib
dT ()
= d
T ()
!
T () = A exp(ib/!)

44

(353)
(354)
(355)
(356)

However, in order to ensure that the eigenfunction is single-values we require

that
T ( + 2) = T ()
A exp(ib/!) exp(ib2/!) = A exp(ib/!)
exp(ib2/!) = 1

(357)
(358)
(359)

This implies that

2b/! = 2m
=> b = m! m = 2, 1, 0, 1, 2,

(360)
(361)

Substituting this into the solution gives

T () = A exp(im) m = 2, 1, 0, 1, 2,

(362)

As usual we find the constant A by normalization. I Spherical coordinates

we integrate over a spherical volume
d = r 2 sin()drdd

(363)

in the range
0"r"
0""
0 " " 2

(364)
(365)
(366)

Therefore, we seek to evaluate the following integral

! ! ! 2
|F (r, , )|2d sin dr 2 dr = 1
0

If the wavefunction is separable we get

!
!
!
2 2
2
|R(r)| r dr
|S()| sin d
0

(367)

2
0

|T (phi)|2 d = 1

and we can normalize each of the factors individually. Therefore,

! 2
! 2

2
(A exp(im)) A exp(im)d = |A|
d
0

45

(368)

(369)


and we get |A| = 1/ 2 and our normalized solution reads
1
T () = exp(im) m = 0, 1, 2,
2

(370)

Solving for the eigenfunctions of L2 is more difficult. We are interested in

solving the following equation
" 2
#"
#

1
1
2
1
2
!
+ cot() +
S() exp(im) = cS() exp(im)
2
2
2

sin ()
2
2
(371)
which gives
d2 S
c
dS
m2
S
=

+
cot

S
(372)
2
d2
d
!2
sin
We can solve this using the power series method using the following form
S() = sin

|m|

()

aj cos()

(373)

j=0

In this way we can obtain a recursive relation for the coefficients

aj+2 =

[(j + |m|)(j + |m| + 1) c/!2 ]

aj
(j + 1)(j + 2)

(374)

Similar to what we did for the harmonic oscillator we most terminate the
power series as some points k, thus, requiring that
c = !2 (k + |m|)(k + |m| + 1) k = 0, 1, 2,

(375)

We know that |m| = 0, 1, 2, and therefore also k + |m|. We can now define
the quantum number as
l = k + |m|
(376)
and the eigenvalues for the square of the angular momentum is
c = l(l + 1)!2
Therefore, the magnitude of the angular momentum is
&
|L| = l(l + 1)!
46

(377)

(378)

We also see that |m| " l and therefore the only allowed values is
m = l, l + 1, l + 2, , 1, 0, 1, l 2, l 1, l

(379)

The general solution is given in terms of the associated Legendre polynomials

'
(1/2
|m|
m 2l + 1 (l |m|)!
Slm = (1)
Pl (cos ), m ! 0
(380)
2 (l + |m|)!
and for m < 0 we omit the (1)m factor. The first few Legrendre polynomials
are given by
P00 = 1
P10 = cos
(381)
P11 = sin
Therefore, the solutions which are eigenfunction of both operators are
1
Ylm (, ) = Sl,m () exp(im)
2

(382)

which are well know functions called spherical harmonics. Thus the eigenvalues are
L2 Ylm (, ) = l(l + 1)!2 Ylm (, ), l = 0, 1, 2, 3,

(383)

and
Lz Ylm (, ) = m!Ylm (, ),

m = l, l + 1, , l 1, l

(384)

Since we can only specify the length of the vector and its projection
& on the
z-axis it can be anywhere on a cone around the z-axis with length l(l + 1!
and projection m!. There are 2l+1 different orientation of this vector since
these are possible eigenvalues for L2 and we say the this is the degeneracy.
Example find the eigenvalues of Y32 and the length and degeneracy of the
angular momentum and list possible values for m.

|L| =

&

3(3 + 1)! =

L2 Y32 = 3(3 + 1)!2 = 12!

Lz Y32 = 2!

(385)
(386)

12!d = 2l + 1 = 2 3 + 1 = 7
m = (3, 2, 1, 0, 1, 2, 3)

(387)
(388)

Do the same for Y34 not possible since m > l.

47

Ladder-operators for Angular momentum

In terms of general angular momentum operators M we know obey the following commutator relations
[Mx , My ] = i!Mz
[Mz , Mx ] = i!My
[My , Mz ] = i!Mx

(389)
(390)
(391)
(392)

The squared momentum operator is given by

M 2 = Mx2 + My2 + Mz2

(393)

and we know that this operator commutes with the components

[M 2 , Mz ] = 0

(394)

We are interested in finding the eigenvalues for M 2 and Mz . We have already

seen this use the power series method but here we will illustrate the solution
using only commutators. We define two new operators
M+ = Mx + iMy

(395)

which we will call the raising operator. In a similar way the lowering operator
is given by
M = Mx iMy
(396)
The product of these two operator gives
M+ M = (Mx + iMy )(Mx iMy ) = Mx (Mx iMy ) + iMy (Mx iM
(397)
y)
2
2
= Mx iMx My + iMy Mx + My
(398)
= M 2 Mz2 + i[My , Mx ]
= M 2 Mz2 + !Mz

(399)
(400)

and in a similar way we find

M M+ = M 2 Mz2 !Mz
48

(401)

and as expected the two operators do not commute. The commutators between these operators and Mz are
[M+ , Mz ] = [Mx + iMy , Mz ] = [Mx , Mz ] + i[My , Mz ]
i!My !Mx = !M+

(402)
(403)

and the same for the lowering operator

[M , Mz ] = !M

(404)

Now we apply these operators and a common eigenfunction of M 2 and Mz

M 2 Y = cY

(405)

Mz Y = bY

(406)

and
First we operate with M+ to get
M+ Mz Y = M+ bY
(Mz Mx !M+ )Y = bM+ Y
Mz (M+ Y ) = (b + !)(M+ Y )

(407)
(408)
(409)

there using M+ on Y we have a new eigenfunction with the raised eigenvalues

b + !. Repeating this gives
MZ (M+k Y ) = (b + k!)(M+k Y ), k = 0, 1, 2,

(410)

In a similar way we get for the lowering operator

MZ (Mk Y ) = (b k!)(Mk Y ), k = 0, 1, 2,

(411)

Thus, we have generated a series of eigenvalues in steps of !

, b 2!, b !, b, b + !, b + 2!, +

(412)

We can now show that these all correspond to the same eigenvalues c for M 2
M 2 Mk Y = Mk M 2 Y + [M 2 , Mk ]Y
= Mk M 2 Y + [M 2 , M ]Mk1 Y + M [M 2 , Mk1 ]Y
= Mk M 2 Y + ([M 2 , Mx ] i[M 2 , My ])Mk1 Y + M [M 2 , Mk1 ]Y
= Mk M 2 Y + M [M 2 , Mk1 ]Y
= Mk M 2 Y
= cMk M 2 Y
49

(413)
(414)
(415)
(416)
(417)
(418)

We know that
Mz Y = bY

(419)

Mz Yk = bk Yk

(420)

and
where bk and Yk are the eigenvalues and eigenfunctions generated by the
ladder operator. Therefore,
Yk = Mk Y
bk = b k!

(421)
(422)

Applying Mz to these eigenfunctions gives

Mz2 Yk = bk Mz Yk
Mz2 = b2k Yk

(423)
(424)

M 2 Yk Mz2 Yk = cYk b2k Yk

(Mx2 + My2 )Yk = (c b2k )Yk , k = 0, 1, 2,

(425)
(426)

Subtracting this gives

since the squared operators can only give nonnegative eigenvalues we have
c b2k ! 0

c ! |bk |

c ! bk ! c

(427)
(428)
(429)

Mz Ymax = bmax Ymax

Mz Ymin = bmin Ymin

(430)
(431)
(432)

M+ Ymax = 0
M Ymin = 0

(433)
(434)

We therefore have

and we require that

50

We can use this to

0 = M M+ Ymax = (M 2 Mz2 !Mz )Ymax
= (c b2max !bmax )Ymax
c = b2max + !bmax

(435)
(436)
(437)

and in a similar way for the lowering operator

c = b2min !bmin

(438)

subtracting these two equations gives us

b2max + !bmax + (!bmin b2min ) = 0

(439)

which is a quadratic equation with the following solutions

bmax = bmin

(440)

bmax = bmin !

(441)

bmax bmin = n!, n = 0, 1, 2,

(442)

1
3
1
bmax = n! = j!, j = 0, , 1, ,
2
2
2

(443)

bmin = j!

(444)

c = b2max + !bmax = j 2 !2 + j!2 = j(j + 1)!2

(445)

and
which we reject since these gives us bmax < bmin and can therefore not be an
acceptable solution. Moreover we know that

This gives us

and
and we find the eigenvalues of M 2 as

The one-particle central-force problem

A very important class of problems are particles which experience a central

force, i.e. a force that is spherically symmetric and thus only depends on the
distance of the particle from origin
F = V (x, y, z)
51

(446)

The hamiltonian for such a system is given by

= (!2 /2m)2 + V (r)
H

(447)

The nabla operator in spherical coordinates are given by

2 =

2
2
1 2
1

1
2
+
+
+
cot

+
r 2 r r r 2 2 r 2
r 2 sin2 2

(448)

2 operator as
where we can introduce L
2 =

2
1 2
2
+
2 2L
2
r
r r r !

(449)

Therefore, we can now realize that for a potential of the type V (r) we have

and

L
2] = 0
[H,

(450)

L
z] = 0
[H,

(451)

and we can therefore have a simultaneous eigenfunction of both the hamiltonian and the angular momentum operators. The eigenfunctions are given
by a radial function times the spherical harmonics
= R(r)Ylm (, )

(452)

Using this in the Schrodinger equations given

"
#
!2 2 2
1 2

+
+
L + V (r) = E (453)
2m r 2
r r
2mr2
"
#
!2 2 2
l(l + 1)!2

+
+
+ V (r) = E (454)
2m r 2
r r
2mr2
"
#
l(l + 1)!2
!2 2 R(r) 2 R(r)
+
+
R(r) + V (r)R(r) = ER(r) (455)

2m
r 2
r r
2mr2
Therefore, the spherical harmonics are universal functions and the potential
is determining the form of the radial solution.

52

10

Noninteracting particles

Up to this point we have only considered solution to problems involving one

particle. Now consider a system consisting of two particles where we will let
q1 denote the coordinates of particle one, and q2 for particle two. For this
system we can write the hamiltonian as
1 , q2 ) = H(q
1 ) + H(q
2 ) + H(q
1 , q2 )
H(q

(456)

where the last term reflects the interactions between the two systems. Since
there is a term that depends on both coordinates we cannot use separation of
variables. However, if we assume that the interactions between the two systems are weak we can neglect that term in the hamiltonian. The Schrodinger
equation for the system is then
1 + H
2 )(q1 , q2 ) = E(q1 , q2 )
(H

(457)

Since the hamiltonian is a sum of terms depending on different variables we

can use separation of variables to solve the equations. Thus, we know that
(q1 , q2 ) = 1 (q1 )2 (q2 )

(458)

E = E1 + E2

(459)

and the energy

This can be generalized to multiple dimensions
=
H

n
%

i
H

(460)

and
(q1 , q1 , , qn ) =

n
)

i (qi )

(461)

And the solution is obtained from the individual Schrodinger equations

i i (qi ) = Ei i (qi )
H

53

(462)

11

The Hydrogen atom

The hydrogen atom contains two particles an electron and a proton and is
thus the simplest two particles system. We can transform the equations into
internal coordinates in term of the distance vector between the particles and
the movement of the center of mass. The center of mass is defined as
R=

m1 r1 + m2 r2
m1 + m2

(463)

and the vector between the two particles are

r = r2 r1

(464)

The individual position of the two particles are then given by

r1 = R

m2
r
m1 + m2

(465)

and

m1
r
m1 + m2
The kinetic energy of the total system is then given by
r2 = R +

1
1
T = m1 |r1 |2 + m2 |rr |2
2
2

(466)

(467)

Inserting the definitions of r1 and r2 we get

"
#"
#
"
#"
#
1
m
m
1
m
m
2
2
1
1
r R
r + m2 R + s
r R +
r
T = m1 R
2
m1 + m2
m1 + m2
2
m1 + m2
m1 + m2
(468)
which we can simplify to
1
1
2 + 1 m1 m2 |r|
2 + 1 |r|
2 = M|R|
2
T = (m1 + m2 )|R|
2
2 m1 + m2
2
2

(469)

where the first term represent the translational energy of the system and the
second term the internal kinetic energy. We now make the restriction that
the potential only depends on the internal motion and not the translational.
For such a potential we can write the hamiltonian as
' 2
(
p
1
1
Pm2
2
2

H = M|R| + M|R| + V (r) =

+
+ V (r)
(470)
2
2
2M
2
54

We can now write down the Schrodinger equation and use separation of
variables
Pm2
M = EM m
(471)
2M
which is the Schrodinger equation for a free particle with mass M which gives
a non-negative energy EM . The remaining energy is found from the following
Schrodinger equation
(
' 2
p
+ V (r) (r) = E (r)
(472)
2

12

The rigid rotor

In the rigid rotor the distance between the two atoms are kept fixed and is
thus a parameter and the potential is zero since the energy is purely kinetic.
We are thus left with the following hamiltonian
=
H

p2
2

(473)

Since the distance r is kept fixed we are left with solving the Schrodinger
equation in terms of , . Since we have no radial part we know that the
eigenfunctions is of the form
= YJM (, )

(474)

where we use J and M to denote the quantum number of rotation. The

Hamiltonian is of the form
=
H

p2
!2
1 2
= 2 =
L
2
2
2d2

(475)

We can now straightforwardly solve for the eigenvalues for the rigid rotor
= E
H

(476)

1 2 M
L YJ (, ) = EYJM (, )
2d2

(477)

1
J(J + 1)!2 YJM (, ) = EYJM (, )
2
2d
E = J(J + 1)B, J = 0, 1, 2, 3,
55

(478)
(479)

where we have introduced the rotational constant B =

difference between two rotational states are then

!2
.
2d2

EJ+1 EJ = [(J + 1)(J + 2) J(J + 1)]B = 2(J + 1)B

56

The energy
(480)