Molecular Spectroscopy

The hydrogen atom

NC State University

Electronic Structure of
Hydrogen
The Schrdinger equation for hydrogen
Separation of variables: Radial and angular parts
Hydrogen
y g atom wavefunctions Expectation
p
values
Spectroscopy of atomic hydrogen

Schrdinger
g equation for hydrogen:
y g
The form of the potential
The Coulomb potential between the electron and the proton is
V = -Ze2/40r
The hamiltonian for both the proton and electron is:

Separation of nuclear and electronic variables results in an

electronic equation in the center-of-mass coordinates:

Separation of variables
It would be impossible to solve the equation
with all three variables simultaneously.
y
Instead a procedure known as separation of variables
is used.
The steps are:
1 Substitute in (r,,)
1.
(r ) = R(r)Y(,)
R(r)Y( )
2. Divide both sides by R(r)Y(,)
3. Multiply
p y both sides byy 2r
2

Schrdinger equation for hydrogen:

The kinetic energy operator
The Schrdinger equation in three dimensions is:
2

2
h

+ V = E
2

The
Th operator
t ddeldell-squaredd is:
i
2
2
2

= 2+ 2+ 2
x
y
z
2

The pprocedure uses a spherical

p
ppolar coordinate system.
y
Instead of x, y and z the coordiantes are , and r.

The wavefunctions of a rigid rotor are

called spherical harmonics
Thesolutionstothe
The
solutions to the and
and equation(angularpart)
equation (angular part)
arethesphericalharmonicsY(, )=()()
Separationofvariablesusingthefunctions()
and()allowssolutionoftherotationalwave
equation.

Wecanobtaina
We
can obtain a and
and equationfromtheabove
equation from the above
equation.

Spherical Polar Coordinates

z

r
r cos()
x

r sin() sin()

r sin() cos()

The volume element in spherical

polar coordinates
To solve the Schrodinger equation we need to
integrate of all space. This is the same thing
as performing
f
i a volume
l
iintegral.
t
l Th
The volume
l
element is:

dV = r 2dr sind d
This integrates
g
to 4,, which is the
normalization constant. 4 stearadians also
gives the solid angle of a sphere.

Separation
p
of variables
Thesphericalharmonicsarisefromtheproduct
of after substituting Y =
ofaftersubstitutingY=

Multiplythroughbysin
py
g y 2/h
/ 2.

Separation
p
of variables
Theoperatorsinvariables and operateonfunction
and respectively so we can write
and,respectively,sowecanwrite

WhenwedividebyY=,weobtain

Now,theseequationscanbeseparatedusing
separationconstantm2.

Separation
p
of variables
Wehavealreadyseenthesolutiontothe equation
from the example of rotation in two dimensions
fromtheexampleofrotationintwodimensions.

whichhassolutions

Nowthatwehavedefinedthevaluesofmaspositive
andnegativeintegers,the
g
g ,
equationisalsodefined.
q

The solution of equation gives

Legendre polynomials
Substitute x =cosandtheequationbecomes:
Substitutex
cosand the equation becomes:

Thesolutionrequiresthat =
with=0,1,2..
Where istherotationalquantumnumber.
Theazimuthal quantumnumberism.
Th
Themagnitudeof..ThesolutionsareLegendre
it d f
Th
l ti
L
d
polynomials
P0(x)=1
P2(x)=1/2(3x
(x)=1/2 (3x2 1)
P1(x)=x
P3(x)=1/2(5x3 3x)

The spherical harmonics as solutions to

the rotational hamiltonian
Thesphericalharmonicsaretheproductofthe
The
spherical harmonics are the product of the
solutionstothe and equations.Withnorm
alizationthesesolutionsare

Themquantumnumbercorrespondsthe
z component of angular momentum
zcomponentofangularmomentum.
Thenormalizationconstantis

The form of the spherical

h
harmonics
i
Includingnormalizationthesphericalharmonicsare

Y00 = 1
4
0
3 cos
Y1 = 4
1
Y1

Y2 =
1
2

Y =

3 sine i 2
Y2 =
8

5 3cos 2 1
16
15 sincose i
8
15 sin 2e 2i
32

Theformcommonlyusedtorepresentpandd
orbitals are linear combinations of these functions
orbitalsarelinearcombinationsofthesefunctions

Euler relation
LinearcombinationsareformedusingtheEulerrelation
e+i =cos +isinei =cos isin
+i +e+i
+i e+i
e
e
cossin

2
2i

Projectionalongthezaxisisusuallytakenusing
z = rcos Projection in the x y plane is taken using
z=rcos.Projectioninthex,yplaneistakenusing
x=rsincosand y=rsinsin

Solutions to the 3-D rotational

hamiltonian

There are two quantum numbers

is the total angular momentum quantum number
m is the z-component of the angular momentum
The spherical harmonics called Y are functions whose
probability |Y |2 has the well known shape of the s, p and
d orbitals etc.
etc
= 0 is s , m = 0
1, 0 , 1
= 1 is p , m = -1,
= 2 is d , m = -2 , -1, 0 , 1, 2
= 3 is f , m = -3 , -2 , -1,, 0 , 1,, 2,, 3
etc.

Space quantization in 3D
z
M = +2
M = +1
M=0
M = -1
M = -2
2
J=2

Specification of the azimuthal

quantum number mz implies
that the angular momentum
about the z-axis is Jz = hm.
This implies a fixed orientation
between the total angular
momentum and the z
component.
The x and y components
cannot be known due to the
Uncertainty principle.

Standing waves on a sphere

These are the spherical harmonics Ylm, which

are solutions of the angular Schrodinger equation.

Orthogonality
g
y of
wavefunctions

IIgnoring
i normalization
li ti we hhave:
s 1
p cos,
cos sincos,
sincos sinsin
d 1/2(3cos2 - 1), cos2cos2, cos2sin2,
cossincos , cossinsin

The differential angular element is sindd/4

The limits = 0 to and = 0 to 2.
The angular wavefunctions are orthogonal.
orthogonal

Orthogonality
g
y of
wavefunctions
For the theta integrals we can use the substitution
x = cos and dx = sind
For example, for s and p-type rotational wave functions we
have

<s|p>

cos sin d =
0

2 1

x dx = x
2

= 1 1 =0
2 2

MAPLE
worksheet on spherical harmonics
Th
The fform off the
h spherical
h i l hharmonics
i Ylm (,)
( ) is
i quite
i
familiar. The shape of the s-orbital resembles the first
spherical harmonic Y00.
Attached to this lecture are three MAPLE worksheets
that illustrate the s,
s p and d orbitals respectively
respectively. The
idea is to obtain an interactive picture of the
mathematical form and the pplots of the functions.
Disclaimer: The spherical harmonics have been
simplified
p
byy formation of linear combinations to remove
any complex numbers.

MAPLE
worksheet on spherical harmonics
Th
The Y00 spherical
h i l hharmonic
i hhas th
the fform off an
s-orbital.

There is only one angular function for

MAPLE
worksheet on spherical harmonics
The Y10 Y11 , and Y1,-1 spherical harmonics have the
form of p-orbitals.

There are three angular functions for

MAPLE
worksheet on spherical harmonics
Th
The Y20 , Y21 , Y2,-1 , Y2,2 andd Y2,-2 spherical
h i l
harmonics have the form of d-orbitals.

There are five angular

g
functions for.

The effective potential: result of

the solution of the angular part
The solutions for the angular
g
ppart results in a
term in potential energy equal to:

This term contains the contributions to the

energy from angular terms.
Together with the Coulomb potential the
effective potential energy is:

The radial equation for hydrogen

Making the abo
abovee appro
approximations
imations wee ha
havee an
radial hamiltonian (energy operator)

l e-/2 L (r)
The solutions have the form: Rn,
=
N

n,ll
n,ll
n,
n,ll
n,
where = 2Zr/na0 and a0 = 44
0h2/me2
Nn,
n,ll is the normalization constant.
Ln,
n,ll(r) is an associated Laguerre polynomial.

Solutions of the radial equation

The normalization constant depends on n an
andd

The associated Laguerre polynomials are:

Normalization of the radial

functions
Each of the radial equation solutions is a polynomial
multiplying an exponential. The normalization is
obtained from the integral:

*
nl

R R nl r dr = 1

The volume element here is r2dr which is the r

r
part of the spherical coordinate volume element
r2sin
sin
drd
drd
d.

MAPLE worksheet
Normalization of the radial functions
A MAPLE worksheet attached to this lecture illustrates
th normalization
the
li ti off th
the first
fi t th
three radial
di l ffunctions.
ti
Th
The
worksheet includes plots of the functions.
When examining a plot keep in mind that you can plot
the wave function or the square
q
of the wave function.
We often plot the square of the wave function, because
the integral of the square of the wave function gives the
probability.
b bilit

Hydrogen 1 s radial
wavefunction
f
ti

n = 1 and = 0 are
th quantum
the
t numbers
b
for this orbital.

1.5

R 1 ,0

The 1s orbital has no

nodes and decays
exponentially
exponentially.
R1s = 2(1/a0)3/2e-/2
For
F n = 1,
1 = 1/a
1/ 0

2.0

1s

1.0

0.5

10

The Radial Distribution in

Hydrogen 2s and 2p orbitals
0.6

n ,l

2s

2pp

0.4

0.2

0.0

10

Radial wave functions for H

The Rydberg
y
g Constant
The energy levels calculated using the
Schrdinger equation permit calculation of the
Rydberg constant.
One major issue is units. Spectroscopists often
use units of wavenumber or cm-1. At first this
~
seems odd, but h = hc/ = hc where is ~the
value of the transition in wavenumbers.

e
1
R=
2 2
2
hc 32
32 0 h
4

in cm-1

The simple form for

H energy levels
Using the Rydberg constant the energy of the
hydrogen atom can be written as:
~

R
E= 2
n
where R = 107,690
107 690 cm-1 .
In units of eV R = 13.6 eV.

Shells and subshells

All of the orbitals of a given value of n for a shell.
shell
n = 1, 2, 3, 4 .. correspond to shells K, L, M, N
Orbitals with the same value of n and different
values of form subshells.
= 0, 1, 2, ... correspond to subshells s, p, d
Using the quantum numbers that emerge from
solution of the Schrdinger equation the
subshells can be described as orbitals.
orbitals

Hydrogenic orbitals
s orbitals are spherically symmetrical. The 1s
wavefunction decays exponentially from a
maximum value of (1/a03)1/2 at the nucleus.
p orbitals have zero amplitude at r =0, and the
electron possesses an angular momentum of
hl(l +1). The orbital with m = 0 has zero angular
momentum about the z axis
axis. The angular
variation is cos which can be written as z/r
leading to the name pz orbital.
orbital

Spectroscopy of atomic hydrogen

S
Spectra
t reported
t d in
i wavenumbers,
b
cm-11
Rydberg fit all of the series of hydrogen spectra
with a single equation,
=R 1 1
n
n
Absorption
p
or emission of a pphoton of frequency
q
y
occurs in resonance with an energy change,
E = h ((Bohr frequency
q
y condition).
)
Solutions of Schrdinger equation result in
further selection rules.
2

Spectroscopic transitions
A transition
t
iti requires
i a transfer
t
f ffrom one state
t t
with its quantum numbers (n1, 1, m1) to another
state (n2, 2, m2).
Not all transitions are possible: there are
selection rules, = 1, m = 0, 1
These rules demand conservation of angular
momentum. Since a photon carries an intrinsic
angular momentum off 1.

Expectation values
The expectation (or average) value of an observable <r> is given
b the
by
th generall fformula.
l

rd
*

<r>=
0

As written the above integral describes the expectation value

of the mean value of the radius, r. Integration over the angular
part gives 1 because the spherical harmonics are normalized.
The volume element can be written d = r2dr. The mean value is:

r r dr =
*

<r>=
0

r 3dr
*

MAPLE worksheet on
Expectation (Average) values
There is a MAPLE worksheet attached to this lecture
that illustrates the use of expectation values. The
example of the position <r> is given for the 1s, 2s and
3s radial wave functions. The expectation value or
average value of r gives the average distance of an
electron from the nucleus in a particular orbital. Since
the 2s orbital has one radial node and the 3s orbital has
two radial nodes the average distance of the electron
from the nucleus is shown to increase as:
<r> for 3s > <r> for 2s > <r> for 1s

The average energy

The expectation (or average) value of the energy <E> is given
b the
by
th generall fformula.
l

H d
*

<E>=
0

since the hamiltonian H is the energy operator. If the wave function

is not normalized this is often written as:

<E>=

* H d

d
*

The Variation Method

The variational theorem
The He atom

The variational theorem

The variation method allows us to obtain an approximation
to the ground state energy of the system without solving
the Schrdinger equation
equation.
The variation method is based on the following theorem:
Given a system with hamiltonian operator H, then if is
any normalized well-behaved function that satisfies the
boundaryy conditions it is true that

*Hd E0
where E0 is the true value of the lowest energy eigenvalue
of H. This important theorem allows us to calculate an
upper bound
b
d ffor th
the ground
d state
t t energy.

Practical significance
The variation method serves as the basis for all methods
that use combinations of hydrogen-like orbitals to solve for
the eigenfunctions (wave functions) and eigenvalues (energies)
of atoms and molecules.
The radial part of the hydrogen-like
hydrogen like wave functions is modified
by a variational parameter, which is minimized. The theorem
allows us to set the derivative with respect to any parameter
equal to zero to find the value of that parameter that minimizes
the energy:

*Hd

Hd = 0

We can be sure that the energy calculated in this way will be

greater than the true energy (an upper bound).

The hamiltonian for H

The electronic hamiltonian for the hydrogen atom consists of a
kinetic energy term for the electron and the Coulomb attraction
of the electron and proton (nucleus).

2
h

2
2m

+
2
Ze
Z
r
1

Of course,
course the nuclear charge of hydrogen is Z = 1 so the
Z is included for completeness. We know that the solutions
Of the Schrdinger equation (H = E) gives energy levels:
n is the principal quantum number
number.
2
a0 is the Bohr radius.
En = e 12

2a 0 n

The hamiltonian for He

For helium the same kinetic energy and Coulomb attraction
terms are present, but there is also a Coulomb repulsion
between the two electrons that must be included.
2

h 12
2m

e2
r 12

2
Ze
r
1

++

2
h

22
2m

2
Ze
Z
r
2

Because of the Coulomb repulsion there is no exact solution

for He. To solve the problem we use two 1s orbitals from the
y g and then apply
pp y the variational method.
solution for hydrogen

The He wave function

The hydrogen 1s wave functions for electrons 1 and 2 are:

f1 = 1 aZ
0

3/2

e Zr 1/a 0, f2 = 1 aZ
0

3/2

e Zr 2/a 0

The aufbau
Th
fb approach
h ffor atoms
t
assumes that
th t the
th total
t t l wave
function for a many-electron atom is just a product of one
electron wave functions. In the present case:

= f1 f2
Note that the hydrogen wave functions are normalized so:
*

f1 f1d =

f2 f2d = 1

Variational approach for the He atom

The He wave function used for the variation method is a
product of two hydrogen 1s orbitals
orbitals. However
However, instead of
the nuclear charge Z we use a variational parameter .

1
r 1/a 0 r 2/a 0
= a e
e
0
3

has a physical interpretation. Since one electron tends to

screen the other from the nucleus, each electron is subject to
a nuclear charge that is less than Z
Z.
The hamiltonian is:
2
2
2
2
e 2 h 2 2 e 2
2
h
e
e
e
H=

+ Z r + Z r + r
2m 1 r 1 2m 2 r 2
1
2
12

Evaluation of the integrals

If we consider only the part of the hamiltonian in parentheses
We have the solution to a hydrogen atom with two electrons
in the 1s orbital.
2
2
e 2 h 2 2 e 2
2
2e
h

1 r

= a
2
2m
2m 2 r 2
2
1
0

where the right hand side is twice the energy of a 1s electron.

Using this result we have:
2
e
*Hd = a
0
2

*d + Z e 2

*d
2
r1 + Z e

*d
2
r2 + e

*d
r 12

The integrals have the following values:

*d = 1 ,

*d

d
r1 =

*d

d
2
=
,
e
r2
a0

*d

d
5 e 2
=
r 12
8a 0

Evaluation of the variational parameter

We have:
2
e
5
*Hd = 2Z + a
8
0
2

We now vary to minimize the variational integral:

2
e
2

5
*Hd =
2Z + a = 0

8
0
2 2Z + 5
8
5
16

The variational energy is:

2
e
5
25
5
*Hd
*H d = Z + Z
=

8
256 a 0
16
2

2 2

e
a0

The variational energy:

comparison with experiment
The experimental ionization energy of He is 24
24.5
5 eV.
eV
Our first guess would be to calculate the energy of the 1s
El t
Electron
iin H
He using
i th
the h
hydrogen
d
energy llevell with
ith a nuclear
l
charge Z = 2, E = -Ze2/a0.
This gives - 2(13.6) eV = -27.2 eV.
Using the value obtained by the variational method we have,
E = -(27/16)e
(27/16)e2/a0 = -(27/16)(13
(27/16)(13.6)
6) eV = -22
22.95
95 eV.
eV
The value is much closer to the true value. In accord with
th variational
the
i ti
l theorem,
th
th true
the
t
ground
d state
t t energy is
i less
l
than that given by variational method.

Summaryy
The hydrogen
y g atom is the only
y atom with an exact solution.
Hydrogen wave functions are used as the approximation
for atomic wave functions in multielectron atoms.
atoms
The variational principle states that any wave function we
choose that satisfies the Schrdinger equation will give
an energy greater than the true energy of the system.
The variation method provides a general prescription for
improving on any wave function with a parameter by
minimizing that function with respect to the parameter
parameter.