Lecture – 6 Radiative transitions and spectral broadening:

The spectral lines emitted by atomic vapors at moderate temperature and pressure show the
wavelength spread around the central frequency. This is known as width of the spectral lines.
In this lecture at first we will understand the origin of radiative transitions.

We will discuss the different mechanism for the broadening of the spectral lines emitted by the
atomic source.
We will find out the reasons for these broadening.

 We now know that, Bohr’s theory described that the emission of radiation from atoms
was from the higher energy state to lower energy state of atom.
 This is known as “quantum jump”
 Bohr tried to describe it through the correspondence principle

According to Bohr’s theory,

2 2 me4
En1  
(n  1)2 h2

2 2 me4
And En  
( n) 2 h 2

2 2 me4 1 1
Thus En1  En  [ 2 ]
h 2
(n) (n  1)2

2 2 me4 2
 for n >> 1
h 2 n3

The emitted frequency En1  En  h n1, n

However, Bohr’s theory fails to describe the mechanism of transitions between the two
stationary states. It also does not provide rational explanation for deriving the intensity and
polarization of the emitted spectral lines.
Einstein transition probabilities:

The first major step to understand the transitions between two stationary states and the
corresponding radiation was taken by Einstein. Let us assume that E1 and E2 are the stationary
energy levels of an atomic system. Let us consider that this system is exposed to a radiation hν.

E2

E2  E1  h

Absorption Spontaneous
Stimulated
emission
emission

E1

Process 1: If an atom absorbs a photon of energy E2  E1  h , it is excited from the lower

energy level E1 to the higher energy level E2. The process is called induced absorption. The
dp
probability per second that the atom will absorb the photon, 12
dt

This is proportional to the number of photons of energy hν per unit volume = the spectral density
of the radiation field  ( )

dp12
So,  B12  ( ) , B12 = Einstein coefficient of induced absorption.
dt

Process 2: The radiation field can induce the atoms to make a transition from excited states E2
to lower energy state E1. Since the system decreases the energy, the extra energy will be
released as the emission of a photon of energy hν. This process is known as induced emission or
stimulated emission. The induced photon of hν will have the same nature as the photon caused
dp
this emission. The probability 12 that one atom emits one induced photon per second is
dt

dp21
 B21 ( )
dt

B21 = Einstein coefficient of induced emission.

Process 3: An excited atom in the excited state E2 can spontaneously jump into the lower
energy states E1 by emitting a photon of energy E2  E1  h

Note: Spontaneous radiation can be emitted in any arbitrary direction. The probability per
second depends on the nature of the stationary energy state and independent of the external field.
spont
dp21
So,  A21
dt

A21 = Einstein coefficient of spontaneous emission and also known as spontaneous transition
probability.

Relation between B12, B21 and A21

Let us assume that the system is having N number of atoms and distributed in different energy
levels Ei such that  Ni  N

At thermal equilibrium of temperature (T), according to Boltzmann distribution,

 Ei
Ni  N 0 gi e kT
Where g i is the degeneracy of level Ei.

In a stationary field,

The number of photons absorbed per unit volume per second = the emission state

B12 N1 ( )  [ B21 ( )  A21 ]N2

N 2  g 2   ( E2  E1 ) kT  g 2   h kT
Using   e   e
N1  g1   g1 

A21
B21
We get,  ( ) 
 g1  B12  h kT
  e 1
 g 2  B21 

The radiation density given by plank’s law,

8 h 3 1 g 
 ( )  3 h
Equating we get, B12   2  B21
c e kT  1  g1 

It implies that with the equal weights g2  g1 , the probability of induced emission is equal to that
of induced absorption.
 8 h3
We also get A21  B21
c3

This provides the number of modes per unit volume and unit frequency interval

8 h3 A21
n( )  and thus,  B21h
c3 n( )

This means that the ratio of the induced to the spontaneous emission rate in an arbitrary mode in
equal to the number of photons in this mode.

Relation between lifetime and spontaneous transition probability

An excited atom in the excited state E2 can spontaneously jump into the lower energy states E1
by emitting a photon of energy E2  E1  h

spont
dp21
So,  A21
dt Ei

Ai2
Ai1
When there are several pathways then E2
Ai0
Ai   Aik
k
E1

The population of the excited state will decrease. E0

So dNi   Ai Ni dt

We get Ni (t )  Ni (0)e Ait

Ni
Where Ni (0) is the population density at t = 0
Ni(0)
The population Ni (0) will be Ni (0) / e after
time  i  1 . This  i represents the mean
Ai
spontaneous lifetime of the level Ei.
Ni(0)/e

 t
Semiclassical approach of radiative transitions:
In this approach, we consider the radiation as classical electromagnetic wave

E  E0Cos(t  kz )

On the other hand, we treat the atom quantum mechanically. That means, the atoms absorb or
emit radiation when they jump between the two quantized states.

Since the dimension of the atom is much smaller (~0.5 nm) than the wavelength of light (~500
nm), we take

E  E0Cos(t ) 
2

E0 it it
e e 
In the dipole approximation, the interaction energy V  p.E  pE0Cos(t ) where the dipole
p  er

The general solution (r , t ) of the time dependent Schrodinger Equation

(r , t )
H  (r , t )  i
t

Can be expressed as (r , t )   Cm (t )m (r )eiEmt /

m

Where m (r ) is the eigenfunction of the time independent Schrodinger equation

Hm (r )  Emm (r )

For two level system, (r, t )  a(t )a (r )eiEat /  b(t )b (r )eiEbt /

Where a(t) and b(t) are the time dependent probability amplitude of the states a and b and

a(t )  b(t )  1
2 2

Substituting in the Schrodinger equation, we get

da(t ) iEat / db(t ) iEbt /

i a e i b e  a(t )V a eiEat /  b(t )V be iEbt /
dt dt

a
 da(t ) i
Integrating over the space we get    a(t )Vaa  b(t )ei ( Ea  Eb )t / 
dt

db(t ) i
And   b(t )Vbb  a(t )ei ( Ea  Eb )t / 
dt

Where Vab   a*V b d  eE  a*rb d

The dipole matrix element Dab  e a*rb d

Since r has odd parity, we get Dab  Dba  0 and Dab  Dba  e a*rb d

This depends on the stationary state wavefunctions a (r ) and b (r ) and need to calculate for
understanding the transitions between the two states.

Intensity of the transition I  Dab

2

Widths and Profiles of Spectral lines

The spectral lines observed from atomic vapors are never strictly monochromatic.

Even with very high sensitive instrument, the observed lines show a wavelength spread around
the line center.

This is known as width of the spectral lines.

Width of the spectral lines

Central frequency  0  ( Ea  Eb ) / corresponding to a transition

The line profile I ( ) around  0 is known as line profile

I0
 1 and  2 where the intensity is the half of the maximum
intensity ( I 0 / 2 )
I0/2
   2 1 is known as the Full Width at Half Maximum /2
(FWHM)

c  c 
Since   then     2  
   1 0 2 
  
The relative half width 
 

Mainly there are two reasons for the broadening of the spectral lines

(a) Width caused by the atomic source

(b) Width arises due to the instrumental limitations

(a) There are basic three reasons for the broadening caused by the atomic source

1. Natural line broadening

2. Doppler line broadening

3. Pressure / Collisional line broadening

Depending on the effect on the individual atoms, there are two types of broadening.

If all the atoms are experiencing the same type of effect, then the broadening caused by this is
known as Homogeneous broadening.

On the other hand, if individual atoms are experiencing different effect then this is known as
inhomogeneous broadening.

1. Natural line broadening

An excited atom can emit the radiation spontaneously. This phenomenon can be treated
classically as damped oscillator discussed in the previous lecture.

The intensity profile

1
I (  0 )  A( ) A* ( )  I 0
(  0 )  ( / 2)2
2

Where I0 is the maximum intensity and   2 . This line profile is known as Lorentzian profile
and can be written as

1 
L(  0 ) 
2 (  0 )  ( / 2) 2
2

In this, full width half maximum (FWHM) =    or   

2

This also can be understood from the Heisenberg Uncertainty Principle

 .E  h 2 where  is the lifetime and E is the uncertainty in energy. So, when  is small,
E is large.

This broadening is known as natural linewidth of the spectral line for the excited state whose
lifetime is finite. The broadening of the spectral line can not be smaller than this E even a high
resolution instrument is used to measure it. This type of bradening is Homogeneous broadening.

1
Natural Width 
Life Time of Excited States

At high pressure, due to collisions life of the excited state is decreased and the broadening occurs.

n0
 ti
1
 ti  time for atom i in the excited state
n0 i 1

lifetime of the
excited state

If collision occurs it looses some excitation energy and for that if ti decreases then the natural width
increased.

For example: If the lifetime of a particular excited state is 10-9 sec then the energy broadening from
Heisenberg uncertainty principle

E t 
1.05 1034
 E   9
J  11025 J
t 10

2. Doppler line broadening

Atoms emitting electromagnetic radiation are not stationary (gas). For an observer in the laboratory frame
of reference, the emission must be considered as coming from a source in motion, so necessary to take
Dopper effect.

Speed V of atom is small compared to c , so it is possible to use classical expression for the Doppler
effect.

Let  be the angle between observation direction & velocity vector, the change of frequency 
between the exact frequency  0 and the frequency  seen by the observer,

V

Detector
0 
   0 V cos  Vx
  
0 0 c c

Vx is the component in the direction of the observer. If we assume that the temperature of the gaseous
source of light is uniform, the distribution of speeds of the atoms is a Maxwell distribution. So the
number of atoms whose velocity Vx is between Vx and Vx  d Vx

dN  N f Vx  d Vx N  Total no. of Atoms

f Vx  is the probability density for the component vx

 M   M 2
f Vx     exp   Vx 
 2 RT   2 RT 

M  molecular weight, R  perfect gas constant

  0 d
Now, Vx  c So, dVx  c
0 0

Let P d is the power emitted in the band frequencies between  and   d is proportional to the
number of atoms between velocity Vx and Vx  d Vx , if proportionality constant is K ,

P d  K N f Vx  d Vx
   0  d
 K N f c c
 0  0
   0 
 K ' f c  d
 0 
   0   M c 2   2 
So, P  K ' f  c   K "exp   
0

 0   2 RT 0 
2

This profile is Gaussian line profile.

P

 D   2 1 , the width at half height of the curve.

K”/2

1 0 2 
  M c 2   2  1
exp   0

 2 RT 0
2
 2 2 0  2 RT 
So the width  D   ln 2 
c  M 
 0  2 RT 
   0     ln 2 
c  M 

 D  T
So, Doppler Width  0
1

M

 
 106 
c 
1
  589.3 nm      0.057 cm1 
  1010

Na gas at 500 K
Natural Line Width

So the Doppler width is much greater than the Natural line width. Doppler broadening is inhomogeneous

broadening.

3. Pressure / Collisional line broadening

For a gas at a given pressure radiating atoms interact with the neighboring atoms via collision
and this affect the emission line width strongly.

For example, an atom A with energy levels E1 and E2 approaches to another atom B. Because of
the interaction, the energy levels get perturbed and the shift of these energy levels occur. Due to
this the line profile gets broadened. This broadening depends on the collision diameter.

1
FWHM = where  0 is the mean flight time between two successive collision.
 0

(b) Width arises due to the instrumental limitations; The basic set up for the emission
experiment is

Monochromator
Detector
 The basic configuration of a monochromator

S1()

S2()

Source f1 slit aperture Dispersing element f2 Screen

dx dn
Linear Dispersion = f ( , f 2 )
d d

Slit width = x1

I
Image width = x1(f2/f1)

Spectral Resolving Power

Diffraction due to aperture

I (  0 )  I (0 )[ Sin((  0 ) / 2)(  0 ) / 2]2

I ( )  I 1 (  1 )  I 2 (  2 )
x2
Rayleigh criterion

0.8 of Imax

x2 = f2(/a) I
Where a is the aperture


And the resolving power =


x
The Grating monochromator.

(i) Light gathering power / numerical aperture / speed of monochromator

Acceptance Angle = d/f1

(ii) The spectral transmission of the optical systems T() or R()

(iii) Spectral resolving power = /

minimum separation  of two spectral lines that can be resolved

(iv) Free Spectral range : wavelength range  in which the wavelength  can be unambiguously
determined from x() =


If N is the no. of grooves per inch and m is the order then  mN


In this lecture we understood the classical and quantum description of the radiative transitions.
We established the relations between Einstein coefficients B12, B21 and A21

We came to know that the minimum spectral line width is governed by the lifetime of the excited
state.

Now we know that the origin of homogeneous broadening and inhomogeneous broadening.

We had briefly gone through the monochromator which is an essential instrument for
spectroscopy experiment.

In this module, we prepare ourselves the basic understanding of quantum mechanics through the
development of concept of atom. In the next module, we will start applying these concepts to
understand various observations of atomic spectroscopy.
 Lecture – 7 Quantum Mechanical treatment of One-electron atoms

In this lecture, we will apply the Schrodinger Equation to the simple system “Hydrogen”
and compare the outcome of the Quantum Theory with the experimental results obtained
from different experiments.

We will also get to know about the “wavefunction” and its use in developing the concept
of the structure of atoms.

Why hydrogen?

 One electron atom and the simplest bound system in nature

 Referring to the adjacent figure -1, the proton (+ve Charge) is at the center and the
electron (-ve charge) is moving around the
center.

 The attractive force between them is Z

Coloumbic in nature and the potential is

Equation -1 z
 Ze2
V  V ( x, y, z ) 
4 0 x 2  y 2  z 2 Where Z is
y
x Y
the charge of the nucleus,

Z = 1 for hydrogen.
X
Figure - 1
 Since it is a two body problem, we
convert it to one body problem by introducing reduced mass

mM

mM

Where m and M are the masses of the electron and proton, respectively.

 So, the total energy of the system = kinetic energy + potential enrgy

1
( p x2  p y2  p z2 )  V ( x, y, z )  E …………………. Equation -2
2

Here, px, py, and pz are the linear momenta and E is the total energy.
 For the quantum mechanical treatment, we will convert the classical dynamical
quantities (px, py, and pz ) to its corresponding quantum mechanical operators

  
px  i , p y  i , pz  i
x y z

E i
t

 Substituting in Equation – 2, we get

 2
2
2 2  
  2  2  2   V  x, y, z   i ………………………. Equation -3
2  x y z  t

 Here, we introduce the WAVEFUNTION to represent the electron.

    x, y, z, t  ………………………. Equation -4

The wavefunction contains the information about the position and the time evolution of
the electronic motion. We will understand more about this later.

So operating equation -2, on the wavefuntion,     x, y, z, t  ,

  2   x, y , z , t   2   x , y , z , t   2   x , y , z , t  
2
  x, y, z , t 
      V  x, y , z    x , y , z , t   i
2  x 2
y 2
z 2
 t
2

 2  V   i
2 t
………………………. Equation -5

2 2 2
  2 2 2
2
is the Laplacian operator.
x y z

This Equation -5 is known as Time dependent Schrodringer Equation.

Since the potential V ( x, y, z ) does not depend on time t, and we are interested to evaluate
the energy of the stationary (time independent) states, we can take this wavefunction as
the explicit dependence of time such as

  x, y, z, t     x, y, z  eiEt /

Substituting this to Equation -5, we get

 2
 2  x, y, z   V  x, y, z   E  x, y, z  ………………………. Equation -6
2

This is the Time Independent Schrodringer Equation.

Now we have to evaluate the stationary state energies ( E ) of the electron in this system
by solving this equation to explain the observed spectra of hydrogen.

Since the potential is spherically symmetric

Ze2 Ze2 Z
V ( x, y, z )    V (r )
4 0 x  y  z
2 2 2 4 0 r

We can convert Equation -6 to its spherical polar 

coordinate (Figure -2) form, z
r
2
 2  r , ,    V  r   r , ,    E  r , ,   y
2 x Y

………………………. Equation -7

Radial distance  r, Polar angle   and X

Azimuthal angle   Figure - 2

The form of the Laplacian operator in Spherical polar coordinates is

1  2   1     1 2
2   r    sin   
r 2 r  r  r 2 sin      r 2 sin 2   2

Using the separation of the variables, we can write the wavefunction as the product form
of the independent variables R  r  ,    ,   

  r , ,    R  r       

Substituting in equation – 7,
2
 1   2 R  1   R  1  2 R 
         V  r  R  ER
2  r 2 r    r 2 sin 2   2 
r sin
r  r 2 sin   

Carrying out the partial differentiation,

 2
    2 R  R     R  2 
         V  r  R  ER
2  r 2 r  r  r 2 sin      r 2 sin 2   2 
r sin

2 r 2
Multiplying the this equation by and rearranging we get,
R 2

 1   2 R  1     1  2  2 r 2
  r    sin    2 
 2  E  V  r    0
 R r  r   sin       sin 2
   

Separating the radial ( R  r  ) and angular (    ,    ) part

1 d  2 dR  2 r 2 1 d  d  1 d 2
 r   
 E  V  
r     sin   
R dr  dr  2
 sin  d  d   sin 2  d 2

Note here that the partial derivative forms are converted to total derivative form. Now
each equation should be equal to a constant, let’s take as .

So, the radial part is

1 d  2 dR  2 r 2
r   2  E  V  r    
R dr  dr 
…………………. Equation -8
1 d  2 dR   2 
r    2  E V  r   2  R  0
r dr  dr  
2
r 

And the angular part is

1 d  d  1 d 2
 sin     
 sin  d  d   sin 2  d 2
sin    d   1 d 2
  sin     sin 2  ………………………. Equation -9
 d  d   d 2

Now, separating the polar and the azimuthal part

sin  d  d  1 d 2
 sin     sin 2
    ml2 ………………………. Equation -10
 d  d   d 2
Here, we have taken that both sides should be equal to a constant m2. Note that we have
three independent equations from equation 9 and 10.

Now let us first consider the azimuthal part (Equation -10)

1 d 2 1 d 2
  ml2  ml2  0
 d 2
 d 2

The general solution of this equation may be written in the form

1 iml
 ml    e ……..………………. Equation -11
2
2

 ( ) ml ' ( ) d   ml ml '
*
Which satisfies the orthonormality condition ml
0

As the einegfunctions must be single valued, i.e.,    which means

eiml 0  eiml 2
And using Euler’s formula 1  Cos(ml 2 )  iSin(ml 2 )

This is satisfied only if ml = 0, ±1, ±2, ..

Therefore, acceptable solutions only exist when ml can only have certain integer values,
i.e. it is a quantum number. Thus, ml is called the magnetic quantum number in
spectroscopy because it plays role when atom interacts with magnetic fields.

Now we will discuss the polar part in Equation 10

sin  d  d 
 sin     sin   ml
2 2

 d  d 

Rearranging, we get

1 d  d      ml2 
 sin  
         0 ……..………. Equation -12
sin  d  d   sin 2  

Let us introduce new variable   Cos , the Equation-12 becomes,

d  2 d      ml2 
 (1   ) 
         0 ……..……………. Equation -13
d  d   1 2 
The Equation-13 has singularities at    1 , which may be eliminated by having a
solution  in the form of

 (1   2 )s / 2 u

Then Equation-13 becomes

d 2u du  s 2 2  ml2 
(1   2 )  2 ( s  1)     u  0
d 2 d  1 2 

Which can be written as

d 2u du  s 2  ml2 
(1   2 )  2 ( s  1)     s 2
 s   u  0 ……..…………. Equation -14
d 2 d  1 2 

The last singular term in Equation-14 can be removed by taking s =  ml  0, and then we
have

d 2u du
(1   2 )  2 (ml  1)    ml (ml  1)  u  0 ……..………………. Equation -15
d 2
d

Which is a regular equation and hence its series solution may be written as

u   ar r ……..………………. Equation -16

r 0

Substituting in Equation-15, yields the recursion relation

(r  ml )(r  ml  1)  
ar  2  ar
(r  1)(r  2)

Requiring that the series be (Equation-16) be limited by a certain power r = q, i.e.

requiring that it be a polynomial of order q, we have to introduce the condition

ar 2  0, ar  0 which requires   (q  ml )(q  ml  1)

Where q = 0, 1, 2, 3, ….

Now we introduce l  q  ml  0,1, 2,3,..... (orbital quantum number) such that

l  ml
  l (l  1)
Then Equation-12 becomes

1 d  d      ml2 
 sin     l (l  1)  2      0 ……..………. Equation -17
sin  d  d   sin  

This is well known associated Legendre differential equation with its solution as
associated Legendre polynomials

l ,ml  Clml Pl ml ( ) ……..………………. Equation -18

Where Clml is the normalization factor and Pl ml ( ) is the associated Legendre polynomial
defined by

d l  ml  ( 2  1)l 
Pl ml  (1   2 ) ml / 2  
d l  ml  2l l ! 
d ml
 (1   2 ) ml / 2 Pl ( )
d ml

Where Pl ( ) is the ordinary Legendre Polynomial. This expression holds for negative
(l  ml )!  ml
values of ml also Pl ml ( )  (1)ml Pl ( )
(l  ml )!

From this we can establish the range of variation of the azimuthal (magnetic) quantum
number ml = 0, 1, 2, 3, ……, l

The associated Legendre Polynomials satisfy the orthonormilization property

2 (l  ml )! 2l  1 (l  ml )!
1

P ( ) Pl ml ( ) d   l ,l  Clml 
ml
l So,
1
2l  1 (l  ml )! 2 (l  ml )!

Then Equation-18 becomes

2l  1 (l  ml )! ml
l ,ml  Pl ( ) ……..………………. Equation -19
2 (l  ml )!

So, we have now two quantum numbers, namely, Orbital (l) and magnetic (ml)

l  0, 1, 2, 3, ...
ml  l ,  l  1, ..., 0, ..., l  1, l

Depending of the value of l and ml, some of the Associated Legendre polynomials are
P00  1
P11  1  cos 2  
1/ 2
P10  cos 

P21  1  cos 2  
1/ 2
P20  1  3cos 2  cos 
P22  1  cos 2 

These functions are

1.5

1.0

0.5

in Deg
45 ° 90 ° 135 ° 180 °

0.5

Now, we can have the total angular part, from Equation-11 and -19

Yl ml ( ,  )  l ,ml ( )  ml ( )
2l  1 (l  ml )! ml
 Pl (cos  ) eiml
4 (l  ml )!
…………….Equation -20

Recap In this lecture, we have learnt the quantum mechanical treatment of hydrogen
atom problem. To do this, we have used the separation of variables method and in
this method we have written the total wavefunction as a product function of the radial
part and the angular part.

Since the coulomb interaction between the nucleus and the electron is radially symmetric,
we have solved the angular part separately.

While solving the angular part of the wavefunction, we have introduced two quantum
numbers namely, azimuthal or orbital quantum number l and magnetic quantum number
ml .

In the next lecture we will solve the radial part of the wavefunction and will construct the
total wavefunction of the hydrogen atom. We will also calculate the energy levels of the
hydrogen atom and will compare it with the observed spectrum.
Lecture - 8 Quantum Mechanical treatment of One-electron atoms : Radial Part

In the previous lecture, we have solved the angular part of the Hamiltonian.

In this lecture, we will take up the radial part of the Hamiltonian.

We will also determine the total wavefunction of the Hydrogen atom and will calculate the
energy levels.

Now, let us solve the radial part (Eqn. 8.8)

1 d  2 dR   2 
 
Ze2    1 
 r    E  R0
r 2 dr  dr   2  4 0 r  r2


Let us first evaluate the ground state (lowest energy) of hydrogen atom.

Assuming the ground state and taking  0 , we get

1 d  2 dR  2  Ze 2 
 r    E  R  0
r 2 dr  dr  2
 4 0 r 
1  2 d 2R dR  2  Ze 2 
 2 r  2r  2 E  R  0 ….... Eqn. (21)
r  dr 2 dr   4 0 r 
d 2 R 2 dR 2  Ze 2 
   2 
E  R  0
dr 2 r dr  4 0 
r

r
Let us try a solution R  r   Ae a0
, where A and a0 are constants.

dR  r  A  r a0 d 2 R A  r a0
 e ;  e
dr a0 dr 2 a02
A  r a0 2 A  r a0 2 A  Ze 2   r a0
e  e  2 E  e 0
a02 ra0  4 0 r 
 1 2 E   2 Ze 2 2  1
  2  2    0
 0
a   4 0
2
a0  r

1 2 E
 2 0
a02
To satisfy this equation for any value of r , 2
…..Eqn. (22)
E
2  a02
 2 Ze2 2
 0
4 0 2 a0
and …..Eqn. (23)
4 0 2 4 0 2
 a0    for Z  1
 Ze2  e2

Let us calculate the values of a0 and Ground State Energy E ,

me m p

me  m p
a0 
1.055 10  34 2

 9.109  1031 Kg
8.988 10  1.6 10   9.109 10
9 19 2 31

 where me  9.109 10 Kg  31

  1.055 1.055
 m p  1.672 1027 Kg   1034341919319
  8.988 1.6 1.6  9.109
 and m p me  o
 0.00531108 m  0.529 1010 m  0.529 A
e  1.6 1019 Coul
1
 8.988 109 nt  m
2

4 0 Coul 2
 1.055 1034 J  sec  0.6582 1015 eV  sec

which is same as Bohr Radius.

Substituting value of a0 in Eqn. (8.22),

2
E
2 a02


1.055 10  34 2


1.113 1068
2  9.109 10   0.529 10 
31 10 2 5.098 1051

0.2183 1017
  0.1364 102  13.6 eV
1.6 1019

This is the lowest energy state of Hydrogen obtained also from Bohr’s calculation.

Now let us calculate the general radial equation,

1 d  2 dR   2 
 
Ze2    1 
 r    E  R0
r 2 dr  dr   2  4 0 r  r2

The radial derivatives simplify if one factor 1 out from function R , taking
r

u r 
R r   …..Eqn. (24)
r

du
r u
dR dr

dr r2
 dR  du
 r2  r u
 dr  dr
d  2 dR  d 2u du du
  r   r  
dr  dr  dr 2 dr dr
1 d  2 dR  2
d u
 2 r r 2
r dr  dr  dr

Substituting,

1 d u  r   2  Ze2    1  u  r 
2

  2 
E    0
r dr 2   4 0 r  r2
 r
…..Eqn. (25)
d 2u  r   2   Ze2    1 
   2  E    u r   0
dr 2   4 0 r  r 2


This is the Schrödinger equation for the particle in one dimension, restricted to r  0 .

 
d u  r   2 E  2 Ze2
2
  1  u r  0
Rearranging   2      
dr 2   4 0 r r 2 
2

 
 Veffective 

This is a kind of potential  for  0  with positive infinity at the origin, then negative potential
and going to zero at large distances. So the minimum of the potential is at some positive r .

For bound states of proton-electron system, E will be a negative quantity.

Now, we will simplify by introducing dimensionless variable,  such as

   r
d     dr
d  2   2 dr 2
 2
d 2u  r   Ze2 2
  1 
  E    u r   0
2 dr 2  4 0 r 2 r2

2
d 2u     Ze2 2
 2   1 
   E   u  0
2

2 d2  4 0  2 2 
2  E d 2u    
2
Ze2 2
2 E   1 
   E   u  0
2 2
d 2
 4 0  2 2
 2 
d 2u     Ze2 1   1 
  1   u  0
d2  4 0 E  2 

d 2u     Ze2 2 E 1   1 
  1   u
d 2
 4 0 E
2
  2 
 Z  e2 1   1 
 1   u
 2 0   2 
2

Z  e2 d 2u        1 
Substituting 0  , we get  1  0   u ..Eqn. (26)
2 0 2 d2   2 

Here, we understand the asymptotic behavior of solution of the equation 8.26.

Case-I: when  is very large (at large separation between proton and electron), we can neglect
the  terms in equation 8.26 and we get,

d 2u   
 u The solution is of the type, u     Ae   Be 
d 2

Since e  becomes infinite for large , we take and hence, u    ~ Ae 

1
Case-II: When  is very small, then is the dominant term, so,
2

d 2u      1
 u  Note  0
d 2
2

d 2u   
The solution,  C 1
 D 
d2

Again, as   0 ;   becomes infinite.

So we take, D  0 , So, for small  , u    ~ C 1

So, we have established that the solution u    decays as e  at large distance and goes as  1

close to the proton (origin).

Now we write the general solution of equation as

u      1e     .....Eqn. (27)

where,     we have to define.

Let us substitute u    into the Eqn. (8.26)

d u d   
  1e     1  e        1e    
d d
 d    
  e       1       
 d 

and

d 2u     d 2    d       1  
 e      2  1     2   1        
d 2
 d 2
d    

Substituting in Eqn. (8.26)

 d 2    d       1  

e    2   1      2   1        
 d2 d    
    1   
  1  0   e   
  2 
d 2    d       1   1 
  2   1      2   1      0       0
d2 d    
d 2    d   
  2 1    0  2   1     0
d 2
d

…..Eqn. (28)
Now, we have to solve this equation 8.28. Let us take a solution of the form,


d    
d 2    
     Cj j So,   jC j  j 1 and   j  j  1 C j  j 2
j 0 d j 0 d 2
j 0

Putting back to Eqn. (8.27)

   

 j  j 1 C  j
j 1
 2   1  jC j  j 1  2 jC j  j   0  2   1   C j  j  0
j 0 j 0 j 0 j 0

Shifting the summation of the  j 1 terms

   

  j  1 jC j 1 j  2   1   j  1 C j 1 j  2 jC j  j   0  2   1   C j  j  0
j 1 j 1 j 0 j 0

For, j  1 , the first two terms becomes zero. So, we start from j  0

   

 j  j  1 C j 1  j  2   1   j  1 C j 1  j  2 jC j  j   0  2   1   C j  j  0
j 0 j 0 j 0 j 0

   j  j  1 C j 1  2   1 j  1 C j 1  2 jC j   0  2   1  C j   j  0
j 0

This is valid, if all the coefficients of  j are zero.

j  j  1 C j 1  2   1 j  1 C j 1  2 jC j   0  2   1  C j  0

 C j 1 
 2 j  2   1    C 0
…..Eqn. (29)
 j  1  j  2   1  j

Let us examine the behavior at large j value. For large j value, we ignore   1 and  0 , so,

2
C j 1  C Taking the value C0 for j  0
 j  1 j
2
C1  C0
1
2 22
C2  C1  C0
2 1 2
2 23
C3  C2  C0
3 1 2  3
2j
C j  C0
j!
  
2j j
      C j   C0   j

Thus, j 0 j 0 j !

 C0 e2 

Returning back in Eqn. (8.27), the general solution,

u      1e     
  1e  C0e 2 
 C0  1e 

Again, the value of u    increases exponentially for large  and cannot be accepted. The
series has to terminate at finite number before reaching the large value of  .

So, we should except, that at some finite value of j , Eqn. (8.29) 2  j   1  0

So,  0 should be an even integer.

Z  e2 Z  e2
We define, 0  2n ;  2n So,  
2 0 2 ;
4 0 2 n

and,

2 E Z  e2
 
2
4 0 2 n
2 E Z 2  2e4
  This is same energy as Bohr formula for Hydrogen putting Z  1 .
 4 0 
2 2 4
n2
Z 2  e4 1
E
 4 0 
2
2 2
n2

Substituting 0  2n in Eqn.8.29 this

2  j   1  2n
C j 1  C
 j  1  j  2   1  j
2  n   1  j   2n
 C
 j  1 2  j  2  j
In fact, the solution of Eqn.8.28 is known as Associated Laguerre polynomials which is of the
form
  1 2 j n  !
j

  L 2 1
 2  Cj 
n   j  1 !  2  j  1! j !
n  1

 1 2 j  n  !
j
 So,
 C j 1 2  n  1 j 
j  0  n   j  1 !  2  j  1 ! j! 
Cj  j  1 2  j  2

which is same as before.

In fact, rearranging Eqn. (8.28) we can get the solution as “Associated Laguerre Polynomials” of
the differential equation of the form,

d2 k d k
2 n   
Z L Z  k 1 Z  Ln  Z   n Lkn  Z   0
dZ dZ

Substituting Z  2 in Eqn. (8.28), we get,

d2 d   Z   0 
Z 2   Z    2  1  1  Z       1    Z   0
dZ dZ 2 

0
n    1
Here, k  2  1 , and 2
2n
    1  n    1
2

So the solution,

  Z   L2n11  Z   L2n11  2 

In this case, the solution (27) has to be rearranged and we get,

u      2  e  L2n11  2 
1

So,
1
 2r  r  2r 
rRn ,  r   u  r     e n a0
L2n 11  
 na0   na0 
….. Eqn. (30)
r  2r  2 1  2r 
 Rn ,  r   N n , e n a0
  Ln  1  
 na0   na0 

Here we have added the normalization constant N n , and absorbed the factor 2 from the
na0
power term of r .
Now, we evaluate the normalization constant N n , from the relation,


 Rn*,  r  Rn,  r  r 2 dr  1
0

2 2 2
 na 
3
 2 r  2r   2 1  2r    2r 
  1
2 n a0
Substituting, N  0 e    Ln 1   d 
 2  0
 na0    na0    na0 

Here, we can use the orthogonality relation,

 n  k !
3


Z
e Z L Z  L
k 1 k
n
k
m Z  dZ   2n  k  1  mn
0 n!

 na0  2n  n  !  2   n   1!

3 3 3
2
So, we get, N n,   1 So, N n,   
 2   n   1!  na0  2n  n  !
3

Normalized Radial Wavefunction,

 2   n   1!  r n a0  2r 
3
2 1  2r 
Rn,  r     e   * Ln  1   ….. Eqn. (31)
 na0  2n  n  !
3
 na0   na0 

Some useful Associated Laguerre Polynomials

L10  Z   1 ; L30  Z   6
L11  Z   4  2Z ; L13  Z   96  24Z
L12  Z   3Z 2  18Z  18

And the first few normalized radial wavefunction for Hydrogen,

Following figures show the plots of the radial function of the hydrogen atom.

3  a
r
R1,0  r   2a e 0
2 0
 1  3 2  r   r 2a0
R2,0  r   a0 1   e
2  2a0 

1  3 2 r  r 2a0
R2,1  r   a0 e
24 a0

2  32  2r 2r 2   r 3a0
R3,0  r   a0 1   2  e
27  3a0 27a0 
 8  3 2  r  r  r 3a0
R3,1  r   a0 1   e
27 6  6a0  a0

4  3 2 r 2  r 3a0
R3,2  r   a0 2 e
81 30 a0
So the total wavefunction, n, ,m  Rn,  r   ,m   m  
From Eqn. (8.20) and (8.31),

 2   n   1 !  r n a0  2r  2 1  2r 
3

  n,    e   Ln  1  
 na0  2n  n   !
,m 3
 na0   na0 
….. Eqn. (32)

 2  1   m ! P m  Cos  
4   m !

Here, n  Principle Quantum Number

 Azimuthal Quantum Number

m  Magnetic Quantum Number

Recap
In this lecture, we have solved the radial part of the Hamiltonian.

We have also determined the total wavefunction of the Hydrogen atom.

The calculated energy levels depend on the principle quantum number n.

However, the total wavefunction of the electron is characterized by three quantum numbers,
namely n, l, ml.
Lecture - 9
Interpretation of wavefunction and modification for Alkali atoms
In this lecture
 Born interpretation of the wavefunction is discussed
 Radial probabilities of finding the electron in different orbit of hydrogen atom are
elaborated
 The angular part of the wavefuction for different orbital is shown
 The departure in the spectra of alkali atom from hydrogen such as lithium, sodium is
emphasized in the next lecture
 The wavefunction calculated for the hydrogen atom in the previous lecture is complex
quantity (includes e iml  ).
This can not be measured by any actual physical instrument. However, it contains all
the information which the uncertainty principle allows us to know about the associated
electrons.
The connection between the properties of the wavefunction ( x, t ) and the behavior of
the electron is expressed in terms of the probability density P( x, t )
 P( x, t ) is the probability per unit length of finding the particle near the coordinate x at
time t.

 According to Max Born, 1962, the probability density P( x, t )  * ( x, t )( x, t ) where

* ( x, t ) represents the complex conjugate of ( x, t )

Born interpretation of the wavefunction:

If at any instant of time ‘t’, a measurement is made to locate the electron with the
wavefunction ( x, t ) , the probability P( x, t )dx of finding a particle at a position
between x and x+dx is proportional to ( x, t ) dx .
2

P( x, t )  * ( x, t )( x, t )  ( x, t ) ……9.1
2

It implies that sign of the wavefunction has no direct physical significance. In the figure-
9.1, the wavefunction has changed its sign but the probability of finding the electron is
symmetric with respect to the nucleus at r/a0 = 0

1.0
x

P x
0.5

0.0

0.5 Fig: 9.1

1.0
6 4 2 0 2 4 6

normalized radial distance r a0

 If the wavefunction changes sign as shown in the figure-9.2, it is called node
( ( x, t )  0 ). The probability of finding the electron (figure-9.3) at node is zero because
P( x, t )  * ( x, t )( x, t )  ( x, t ) ……9.2
2

Node
Node
+

Wavefuntion of the Probability of finding the

electron electron
Fig: 9.2 Fig: 9.3

In the previous lecture, we have evaluated the wavefunction of the electron in Hydrogen
atom as

 2   n   1!  r n a0  2r  2 1  2r 
3

  n,    e   Ln  1  
 na0  2n  n   !
, ml 3
 na0   na0 


2  1   m !
P m  Cos  
4   m !
……9.3

  n,l ,ml (r, ,  )  Rn,l (r )Yl ml ( ,  )

Where n  principal quantum number = 1, 2, 3, 4,….

l  azimuthal quantum number = 0, 1, 2, ….., n-1
and ml  magnetic quantum number = -l, -l+1, …-2,-1,0, 1, 2, ….,l+1=2l+1 values
Z 2  e4 1 13.6 eV R
And the Energy En      ……9.4
 4 0  2 2 n
2 2 2
n n2
The energy depends only on n, but the functional form of R(r) depends on both n and l,
and so we write the radial wavefunction as Rn,l(r) and angular part Y depends on l and ml.
Following table provides the energy and the nomenclature of the states.

Principal Magnetic
Orbital quantum
quantum nomencleture quantum Energy
no.
no. no.
n=1
l = 0 (s subshell) 1s state ml = 0 -13.6 eV
(K shell)
l = 0 ( s subshell) 2s state ml = 0
n=2 2p state ml = -1
-3.4 eV
(L shell) l = 1 ( p subshell) 2p state ml = 0
2p state ml = 1
l = 0 ( s subshell) 3s state ml = 0
3p state ml = -1
l = 1 ( p subshell) 3p state ml = 0
3p state ml = 1
n=3
3d state ml = -2 -1.51 eV
(M shell)
3d state ml = -1
l = 2 ( d subshell) 3d state ml = 0
3d state ml = 1
3d state ml = 2

In the following figure-9.4, we plot the radial functions Rn,l (r ) , the reduced radial
,l (r )  (U n ,l (r )) for
functions U n,l (r )  r Rn,l (r ) , and the radial probability densities Pnrad 2

different states of hydrogen atom. We will also see the plot for different orbitals of
hydrogen atom.

The first orbit n = 1, l = 0 and ml = 0, the K shell

 In this plot we can see the effect of the factor r in U1s (r )  r R1s (r ) . Here, R1s(r) goes
to 2 a0 (Bohr radius) at r = 0, while U1s(r) goes to zero. The factor of r in U1s(r) also
introduces a peak at 1 a0.
 There is no node for 1s state.
 The probability density P1rad
s ( r ) goes to zero at r = 0, it means that the probability of

finding the electron at the nucleus is zero. P1rad s ( r ) shows also a peak at 1a0 which is the
same as Bohr radius and the peak value is 0.54.
 Conceptually, peaks in Pnrad ,l ( r ) are radii near which an electron in a state n,l,ml is

most likely to be found.

 Because of the gradual decay of Pnrad ,l ( r ) on the large-r side of this peak, the calculated

mean radial position turns out to be larger than the location of the peak
 Following figure is the 1s orbital
2.0
R1s

U1s
1.5
P rad 1s

1.0

0.5

0.0 1s orbital
0 1 2 3 4 5 6

normalized radial distance r a0

Figure-9.4 Figure-9.5

The second orbit n = 2 ( L shell), l = 0, ml = 0 and l = 1, ml = 0, 1

 The 2s radial function in the figure-9.6 decays as r more gradually than U1s(r).
Moreover, the 2s radial probability density has two peaks: one at 0.76 a0 and next one at
5.24 a0.
 The height of the peak nearest the nucleus, 0.052, is much smaller than that of the
outer peak, 0.19. The presence of a small peak in P2rad
s ( r ) relatively near the origin is
called penetration.
0.8

R2s
0.6
U2s
0.4
P rad 2s
0.2

0.0

0.2

0.4

0.6
0 5 10 15 2s orbital
normalized radial distance r a0

Figure-9.6

 The 2p functions in this figure-9.7 differ 0.5

R2p

strikingly near the origin from the 1s and 2s 0.4 U2p

P rad 2 p
functions. Because of the l = 1 barrier term in the 0.3

r radial equation, P2rad

p ( r ) rises from zero. 0.2

 U2p(r) has a classically forbidden region near 0.1

the origin. 0.0

0 5 10 15

normalized radial distance r a0

Fig 9.7
 Following figures are three px, py and pz orbitals.

py orbital
px orbital

Figure-9.8 pz orbital

To compare the differences between the functions U n,l (r )  r Rn,l (r ) and

,l (r )  (U n ,l (r )) for the n = 1 and n = 2 states of hydrogen, they are plotted on the
2
Pnrad
same graph as shown in the following figures-9.9 and 9.10.

 The increase in l by 1 from 2s to 2p states means that neither U2p(r) nor P2rad
p ( r ) have

nodes. Asymptotically, both functions decay at the same rate as their 2s counterparts,
because the decay constant for a pure- Coulomb potential energy doesn't depend on l.

 The sole peak in P2rad

p ( r ) occurs at r = 4 a0, where its value is 0.19. Interestingly, the

mean radius of 2p state = 5 a0 is 1a0 smaller than that of the 2s state.

 In the plots of reduced radial functions U1s(r), U2s(r) and U2p(r), note the differences
in these functions rise from 0. The functions U1s(r) and U2s(r) rise like r, in which U1s(r)
is faster than U2s(r) while U2p(r) rises like r2.

Radial Probability densities

Reduced Radial functions 0.6
0.8
1s
1s 0.5
0.6 2s
radial probability density

2s
reduced radial function

2p
0.4 2p
0.4

0.2
0.3
0.0
0.2
0.2
0.1
0.4

0.6 0.0
0 5 10 15 20 25 0 2 4 6 8 10 12 14
normalized radial distance r a0 normalized radial distance r a0

Figure-9.9 Figure-9.10
 The third orbit n = 3 ( M shell), l = 0, ml = 0 and l = 1, ml = 0, 1 and l = 2, ml = 0, 1, 2

The general features are from the following graphs in figure-9.11:

 U3s(r) has two nodes, U3p(r) has one, and U3d(r) has none.

 The 3s radial probability density has two regions fairly near the origin where there is a
small but nonzero chance of finding the electron.

 The 3s state is the most penetrating, because its radial function is unaffected by a
barrier, while the 3d, which suffers the strongest barrier, is the least penetrating.

 Since the number of nodes = n - l – 1 decreases with increasing l, small l radial

functions have the most nodes.

 Since these nodes are radii where the probability density is zero, radial probability
densities for low- l are characterized by small regions of non-zero probability very near
the nucleus.

2.0 0.4
R3s R3p
1.5
U3s U3p
0.2
1.0 P rad 3s P rad 3 p

0.5 0.0

0.0
0.2
0.5

1.0 0.4
0 5 10 15 20 25 0 5 10 15 20 25

normalized radial distance r a0 normalized radial distance r a0

0.4
R3d

U3d
0.3
P rad 3d

0.2

0.1

0.0
0 5 10 15 20 25 30

normalized radial distance r a0

Figure-9.11
 The following graphs in figure9.12 show the comparison of reduced radial functions and
probability densities of n = 3 states

 The n = 3 states show that as l increases, the outermost peak moves inward, to smaller
radial distance.

 The magnitude of each peak increases as the radial distance increases. This increase
occurs because as l increases by one unit, the probability density, which must remain
normalized to unity, looses one inner peak.

 In spite of all these variations, the energies of all these n = 3 states is the same, E3 =
1:51 eV.

 The range of r values required to plot all of the radial probability density for the n = 3
states is more than twice for states with n < 3.

Reduced Radial functions Radial Probability densities

0.4 0.12
3s 3S
3p 0.10 3P
radial probability density
reduced radial function

0.2 3d 3D
0.08

0.0 0.06

0.04
0.2
0.02

0.4 0.00
0 5 10 15 20 25 30 35 0 5 10 15 20 25 30 35
normalized radial distance r a0 normalized radial distance r a0

Figure-9.12

The five d – orbitals are shown in figure-9.13

dxy orbital dyz orbital dxz orbital

 Figure-9.13
d x2  y 2 orbital
d z 2 orbital

Following graphs in figure-9.14 show the comparison of the probability densities for n =
1, 2, 3, 4 states.

 All s-state radial probability densities for n = 1, 2, 3, and 4 behave the same way near
the origin. None suffer the l barrier, so all have peaks near the origin.

 Because the number of nodes in an s state function increases by one with each unit
increase in n, the number of peaks also increases by one.

 Only for the 1s state has a large peak near the origin; the magnitudes of the near-origin
peaks in radial probability density for n > 1 decrease rapidly with increasing n.

 Consequently the probability of finding the electron far from the nucleus increases
appreciable as n increases.

0.6 0.20
2p
0.5 1s
3p
2s 0.15
Probability density
Probability density

3s 4p
0.4
4s
0.3 0.10

0.2
0.05

0.1

0.00
0.0 0 10 20 30 40
0 10 20 30 40
normalized radial distance r a0
normalized radial distance r a0

Figure-9.14
Main features to remember

 l = 0, s-states do not vanish at r = 0.

 l 0, states vanish at r = 0 and have their maximum probability amplitude further out
with increasing l.

 The size, position of peak probability, scales with ~ n2.

 The l = 0 function crosses the axis (n − 1) times i.e. it has (n − 1) nodes.

 l = 1 has (n − 2) nodes and so on.

 Maximum l = n − 1 has no nodes (except at r = 0)

Page-12
Stern-Gerlach Experiment

In 1922, Stern and Gerlach launched a beam of Silver (Ag) atoms through a non-uniform
magnetic field and detected them at a screen as shown in the figure-9.15.

Silver atom Beam splits

source into two

Magnet Screen Gerlach's postcard, dated 8 Feb,

1922, to Niels Bohr showing a
photograph of the beam splitting,
Figure-9.15

 Classical physics does not predict distinct spots. Distinct spots mean the magnetic
moment is quantized.

 This can not be due to orbital magnetic moment because orbital magnetic quantum
number is odd, we would expect odd number of spots.

 This marked the discovery of the electron spin. A new type of angular momentum,
with a quantum number that can take on only two values:
s  1 , ms   1
2 2
This new kind of angular momentum is known as SPIN.
This spin sometimes visualize by the classical spin picture as shown in figure-9.16.

However, this “spinning” ball picture

shown in figure-9.16 is not realistic,
because it would require that the tiny
electron be spinning so fast that parts
would travel faster than c.
So the spin is another type of angular
momentum. ms = -1/2
So, we need FOUR quantum numbers ms = +1/2
to specify the electronic state of a
hydrogen atom
n, l, ml, ms (where ms = -1/2 and +1/2) Figure-9.16

Recap
In this lecture, we have learnt

 Born interpretation of the wavefunction is that the wavefunction has no direct physical
significance, only the probability of finding the electron is important.

 Radial probabilities of finding the electron in different orbit of hydrogen atom are
different, s orbits is the most penetrating.

 Electron in an atom can be designated by FOUR quantum numbers.

 n, l, ml, ms (where ms = -1/2 and +1/2)

Lecture – 10 ALKALI SPECTRA

In the previous lecture we have learnt the quantum mechanical treatment of hydrogen
atom. The similar picture is not able to explain the alkali atoms, the other elements in the
first group of periodic table.
Here, we will discuss the development of the theory to explain the alkali spectra.

We will also elaborate the concept behind the modification of the potential required to
explain the observation in alkali atoms.

The absorption spectra of alkali vapors (Such as lithium, sodium) appear quite similar in
many respects to the absorption spectrum of H atom. They are only displaced to a
considerable extent, toward longer wavelengths. These spectra also consist of a series of
lines with regularly decreasing separation and decreasing intensity.

 It cannot, however, be represented by a formula completely analogous to the Bohr

formula. On the other hand, since the lines converge to a limit, we must be able to
represent them as differences between two terms.
Rydberg formula,
R
  TPS  where m  2,3
m  p
2

p is a constant, known as Quantum Defect. TPS is known as series limit. This series is
known as Principal series.
 Other series, in addition to this, may be observed for the alkalis. They are diffuse,
sharp and Bergmann series.
R
Sharp Series   TSS  m  2,3
m  s
2

R n  0,1, 2,3
Diffuse Series   TSS  m  3, 4 Selection rules:
m  d    1
2

R
Bergmann Series   TBS  m  4,5
m  f 
2

As an example, sodium energy levels and transitions are given in figure-10.1

Bergmann series

Sharp series Diffuse series

Principal series

Figure-10.1
Sodium atom energy levels and transitions
As a specific example, we consider the alkali metals such as lithium, sodium and
potassium, which come from group I of the periodic table. They have one valence
electron outside filled inner shells. They are therefore approximately one-electron
systems, and can be understood by introducing a phenomenological number called the
quantum defect to describe the energies.

Let us consider the sodium atom. The optical spectra are determined by excitations of the
outermost 3s electron. The energy of each (n; l) term of the valence electron is given
by:

R
En,l   ……….10.1
(n   (l ))2
Where n  3,  (l ) is the quantum defect.

Nucleus +11e
3s

1s
2s

valence electron 2p

Sodium Atom Z = 11
Figure-10.2

The quantum defect  (l ) was introduced empirically to account for the optical spectra. In
principle it should depend on both n and l, but it was found experimentally to depend
mainly on l as given in the following table.

Values of quantum defect for sodium

l n=3 n=4 n=5 n=6

0 1.373 1.357 1.352 1.349
1 0.883 0.867 0.862 0.859
2 0.010 0.011 0.013 0.011
3 0.000 -0.001 -0.008

The dependence of the quantum defect on l can be understood with reference to the figure
where the radial probability densities for the 3s and 3p orbitals of a hydrogenic atom with
Z = 1 are plotted with respect to normalized radial distance.

An individual electron in sodium atom experiences an electrostatic potential due to the

Coulomb repulsion from all the other electrons in the atom. Ten out of eleven electrons
are in closed sub-shells, which have spherically-symmetric charge clouds. The off-radial
forces from electrons in these closed shells cancel because of the spherical symmetry.
Hydrogen radial probability distribution (figure-10.3) is expected to be a reasonable
approximation for the single valence electron of sodium.

 We see that both the 3s and 3p orbitals 0.6

penetrate the inner shells, and that this 0.5 1s

penetration is much greater for the 3s 2s

Probability density
0.4
electron. 3s
0.3

 The electron will therefore see a larger 0.2

effective nuclear charge for part of its orbit, 0.1

and this will have the effect of reducing the 0.0

0 5 10 15 20 25 30 35
energies. normalized radial distance r a0

The energy reduction is largest for the 3s Radial Probability densities

electron due to its larger core penetration. 0.12
3S
0.10 3P

radial probability density

3D
0.08

0.06

0.04

0.02

0.00
0 5 10 15 20 25 30 35

normalized radial distance r a0

Figure-10.3

The effect of this penetration results in the shift of energy levels. A comparison with the
hydrogen energy level is shown in figure-10.4.

Hydrogen energy levels Sodium energy levels

Figure-10.4
We can draw the conclusions that,

 Energy levels with different have different energies. In other words degeneracy
removed.

 From the hydrogen atom energy levels, it cannot be described, because energy
depends on “ n ” only.

Classical Explanation
Penetrating and Non-Penetrating Orbits as shown in figure-10.5:
1) Non-Penetrating orbits
The first is the case when the outer electron has a non penetrating orbit, as in the
figure. If its accepted that the mean
symmetry of the cloud formed by  Z  1
-e
electrons is similar, the electron experiences
the electrostatic potential of the nuclear
charge of Ze and of the spherical
distribution of charge  Z  1 . The
discussion presented for the hydrogen atom
remains valid. (Z-1)e

2) Penetrating orbit
On the other hand, if the orbit of the outer electron penetrates inside the core of
the atom, the problem is much more complex, simple solution by Somerfield, is
this,
1 e
Vext  " r " Large -e
4 0 r
1 Ze
Vin   Const. " r " Small
4 0 r

(Z-1)e

Figure-10.5
Quantum Mechanical Calculation

1 e2  b 
Form of the potential energy, V  r    1   …………….10.2
4 0 r  r 
This form represents the potential energy requirement at large distance,
1 e2
V r   
4 0 r
Z e2 1
and at small distance, V  r   
4 0 r
This potential with respect to radial distance is shown in figure-10.6

1 e2  b 
 1  
4 0 r  r 

0
1 e2

4 0 r 2
Potential V r

1 Ze2

6 4 0 r

10
0 1 2 3 4 5

Radial distance r

Figure-10.6
Since this is radial dependence and we need to solve only radial equation of the
Schrödinger equation of hydrogen atom problem
1 e2  b 
V r    1  
4 0 r  r 
c b 1 2
 1   where, c   e
r r 4 0
Now, the Hamiltonian for one electron atom,
2
H  2  V  r 
2
2
c b
 2  1  
2 r r
2
c b
  2   1    E
2 r r
2  c b 
  2  2 
E   1     0
 r r  ………..10.3
The radial equation:
d 2   2 2
 2 E 2
c b   1 
1     R(r )  0
dr 2
 r r r2



d 2   2 2 c 2 c b
  2 E  2  2 2 
  1 
2 2  R(r )  0
dr  r r r  …………10.4

2 E 2 c
Taking A   2
; B 2
and substituting in equation 10.4

d 2  B  B b    1 
2
 A   0
dr  r r2 
Let , *
 *
 1   B b    1

d 2  B  B b    1 
* *

So,  A   0
dr 2  r r2 

Same radial equation as in hydrogen atom, solution with n* where n*  *
 p 1
*
 *
 1    1  B b

  2
 * 2
   *
  Bb
R R   *
  *
 1  B b
E 
n  * 2
  p  1
2
* Bb Bb
  
 1 2 1
*
n   p 1 Now,
B b
So, n*  *
 p 1  *
 n b 1
 2 
1 a1  1
 n*  n    *
 n 2 2
Rhc
En ,  2
 b 1 
n 
 a1  1 
 2

Note that : This energy expression is dependent on both n and l

Maximum l -> small correction

Small l -> correction term is large
Rhc
En,   2
 Bb 
 n  
 2  1
Now we know
E  h
c 1 R
   En,   cm1
   Bb 
2
n  
E
hc


1

 cm1  
E
hc
 2  1

Where R  109,728.7 cm1

Conversion
ergs / molecule Cal / molecule electron volts
1 16
1cm 1.9858 10 2.8575 1.23954 104

Take an Example:
Lithium : ionization potential : 43, 486 cm1 or, 5.39 eV
109728.7
43486 
 2  B b 2
  2  B b   2.5233
2

 2  B b  1.588
 B b  0.41

109728.7 109728.7
E2,1   31603.8 cm1 E3,0   16357.6 cm1
 0.41 
2
 3  0.41 2
2 
 2 
109728.7 109728.7
E3,1   13383.7 cm1 E4,0   8513.9 cm1
 0.41 
2
 4  0.41 2
3 
 3 
109728.7 109728.7
E4,1  2
 7351.8 cm1 E4,2  2
 7148.1cm1
 0.41   0.41 
4  4 
 3   5 

109728.7
E4,3  2
 7063.4 cm1
 0.41 
4 
 7 
 l=0 l=1 l=2 l=3
-1
5000 cm
4f
-1 4p 4p
10000 cm 4s

15000 cm-1 3p 3d
3s
20000 cm-1

25000 cm-1

30000 cm-1 2p

35000 cm-1 Figure-10.7

40000 cm-1
2s
45000 cm-1

Recap

In this lecture, we have learnt that

 The departure in the spectra of alkali atom from hydrogen such as lithium, sodium is
that the energies are not only dependent on n but also l.

 The modification of the potential of electron in such multielectronic atoms is that the
energy correction term is large of small l values.
Lecture – 11 Helium Atom
In this lecture we will extend the problem to more than one electron atoms. We will start with the
simple one such as He atom.

The quantum mechanical calculations of the energy levels in different approximations are
discussed.

From the ionization energy i.e the energy required to remove one electron from Helium atom, the
ground state energy of Helium is calculated to be -79.0eV.

We use this information to check the different method approximation for calculating the Helium
atom energy levels.

The emission spectra of He consists of a number of series in the visible region of the spectrum as
well as in the near & far UV regions.
There are twice as many line series as for the alkalis; two principal series in the visible and near
UV, as well as two diffuse, two sharp and two fundamental series.
This observation cannot be described by simple concept from hydrogen atom.

When more than one electron is present, the Hamiltonian for an atom in free space becomes
2
Z e2 e2
H 
2me
 i2  
i i ri

i  j rij

 TE  VEN  VEE ……..11.1

VEN is the Coulomb interaction between the nucleus and the electrons. VEE is the
electrostatic repulsion of the free electrons, summed over all pairs i and j at separation rij . This
equation (1) does not contain spin part, we assume that such effects can be treated separately.
2
Equation (1) contains terms e for interelectronic repulsions that are not present in the
rij
Hamiltonian for hydrogen like atoms.
Because of these terms, the motion of each electron affects the motion of every other
electrons, and the wave equation for polyelectronic atoms cannot be solved exactly.
Various approximate methods of solution exist. Most methods start by assuming that
complex atoms can be “built up” by feeding electrons successively into atomic orbitals (AOs).
That is, every electron in an atom is assigned a wave function i , defined by a set of quantum
numbers.
The wave function for the whole atom is written in terms of these electron wave
functions i . The best sets of wave functions i are those for which the residual difference
between the calculated energy of the whole atom and the actual energy is as small as possible.
 Independent Particle Model :

One-Electronic Wave Functions

A crude method, zeroth order approximation to the i is obtained by ignoring altogether
the terms VEE in (1), giving the Hamiltonian

2 N N
Z e2
H 
2me
 i2   ri
i 1 i 1
………………… .

Then, in the approximation in which electron spin is neglected, the eigen functions of this
Hamiltonian are products of the occupied single electron orbital wave functions i for the N
electrons,
 1, 2,...., N   1  r1 1 1  2  r2 2 2  .... N  rN  N N 
………. .
Since interactions between the electrons are ignored, each electron moves independently of the
others in the electrostatic field of the nucleus alone. The i is therefore the hydrogen like
wavefunctions, the eigen values of Hamiltonian are the sum or the individual energies Ei for the
electrons in hydrogen like orbitals:
E  E1  E2  ....  EN
` ………… .

Let us take the example of Helium (Z = 2) that consists of two electrons as shown in the fig.-11.1

In this approximation, Hamiltonian ,

2
Z e2 2
Z e2
H  12    22 
2m r1 2m r2 …………… .

e r12 e
a b

r1 r2
Figure-11.1

Schrödinger equation, 2e

 2 2
Z e2 Z e2 
So,   1  2      r1 , r2   E   r1 , r2 
2 2

 2m 2m r1 r2 
………….11.6
Here we take a  r1  and b  r2  are the one electron wavefunction as in hydrogen atom.

  r1 , r2   a  r1  b  r2 
 2
Z e2 
    a  r1   Ea a  r1 
2
 1
 2m r1 
 2
Z e2 
 2   b  r2   Eb b  r2 
2

 2m r2 
E  Ea  Eb ………..11.7

Two electrons “a” and “b” move independently of each other and the total energy of the system is
simply sum of the energies of non-interacting particle.

a  r1   Rn l  r1  Yl m 1 , 1 
11 1 1

b  r2   Rn l  r2  Yl m  2 , 2 
22 2 2

Z 2 m e4 Z2 m e4
En     EH where, EH   13.605 eV
n2 2 2 n2 2 2

The ground state energy of Helium (when both the electrons are in 1s level)

4 4
E  Ea  Eb   2
EH  2 EH  8EH  108.8 eV
I I

The experimental value of the ionization energy i.e. the energy required to remove one electron
from Helium atom = 24.63 eV

When one electron is removed then the energy of ionized Helium ion (He+)

= -Z213.6 eV =-54.4 eV

So the ground state energy of Helium = -54.5 eV - 24.63 eV = -79.03 eV

Thus, Atomic energies calculated in this manner are the poor approximation to the actual eigen
values.
However, the calculated energies and wavefunctions can be improved by introducing the
interelectronic repulsion terms VEE as a perturbation.

Considering electron repulsion:

2 2
Z e2 Z e2 e2
H  12  22    ………..11.8
2m 2m r1 r2 r12
We will consider the first order perturbation theory. In this approximation, we take unperturbed
Hamiltonian as

2 2
Z e2 Z e2
H0      
2
1  2
2
2m 2m r1 r2

e2
And consider the perturbed Hamilrtonian as H 
r12

Substituting in the Schrodinger Equation

 H0  H  a  r1  b  r2   E a  r1  b  r2 
We are interested to calculate the ground state energy. So both the electrons are in 1s level.

So, n = 1, l = 0 and m = 0 for both the electrons. Let us take the ground state wavefuntion of the
hydrogen atom for each electron.
3
1  Z  2  Zr a0
nl m  100  r     2e
4  a0  1 Z
3
 Z  r1  r2 
100  r1  100  r2     4e
a0

4
3
1  Z  2  Zr1 a0  a0 
100  r1     2e So,
4  Z  r1  r2  
 a0 
3
1  Z   
   e  
a0

  a0 
3
1  Z  2  Zr2 a0
100  r2     2e
4  a0 

Evaluating,

e2 e2
  100
*
 1  100  2 
r  *
r 100  r1  100  r2  d1d 2
r12 r1  r2
2 Zr1 2 Zr2
Z 6 e2   1
 2 6  d 1 e a0  d e a0

 a0 r1  r2
2

1  r 
   2  P  cos   for r1  r2 Z
1  r1  r1 

r1  r2  1  r 
    P  cos   for r2  r1
1

 r2  r2 
r1
  between r1 & r2
 r2

Figure-11.2
d 2  r22 dr2 sin  d d
27r1 27r2
1  2 
a0 a0

 1 1 1   
   22 d 1 e 2    2     cos   sin  d d 
e2 Z e2 
 1  1 0
1  1  
      
2
d sin d d e   
32 a0
2 1 1 1 1 1
r12  1  1  
   2 d  2 e          cos   sin  d d 
2  2

 1 2  2 
Z e2  1 1 2    
    2 e d 2   2 e 2 d 2 
 1 
 2 2
d 1 sin 1 d1 d1 e 2

8 a0  1 0
1
1 
5 e 2 5Z e2
 Z  EH where, EH   13.605 eV
8 a0 4 2a0

According to first order perturbation theory the ground state energy of He,

5Z 10
Eground  8EH  EH  8EH  EH
4 4
 108.84  34.01  74.83 eV
Experimental  79.0 eV
Error  4.2 eV

Variational Method
  r1 , r2   a  r1  b  r2 
Trial wavefunction,  Z 3   Zr1 a0  Zr2 a0
 3 
e e
  a0 
2
The effect of the repulsive term e , is to reduce the nuclear charge on each electron. One way
r12
to accommodate this is to assume hydrogen like wavefunction corresponding to effective nuclear
charge Z  , which will be assumed to be the variable parameter. We assume the (trial) normalized
wavefunction,

 Z 3   Z r1 a0  Z r2 a0
  r1 , r2    3 
e e
  a0 
Z  2;

 is normalized, so we have to minimize the integral

E  Z      * H  d 1d 2
 2
2 1 1  e2 
   *    1 2
 2
  2
 Z e       d 1d 2
 2 m  r1 r2  r12 

Since   r1 , r2  is the solution of

 2
Z  e2 
      r1 , r2    Z  EH   r1 , r2 
2 2
 1
 2 m r1 

 Z 2 e 2 Z 2 e 2 Z e 2 Z e 2 e 2 
E  Z      *   Z 2 EH  Z 2 EH        d 1d 2
 r1 r2 r1 r2 r12 
  1 1  e2 
   *  2Z 2 EH   Z   Z  e2       d 1d 2
  r1 r2  r12  ……..11.9

   2Z  E  d d  2Z 2 EH
* 2
1st integration: H 1 2

1 1
   Z   Z  e     d 1d 2
* 2

 r1 r2 
1 1
  Z   Z  e 2   *     d 1d 2
 r1 r2 
 *
2nd integration:   Z   Z  e 2 2  d 1d 2
r1
2Z 
  Z   Z  e2  4 Z   Z   Z  EH
a0
e2
where, EH 
2a0

e2 5
   d1d 2  Z EH
*
3rd Integration:
r12 4

Substituting in equation-11.9,
 5
E  Z    2Z 2 EH  4Z   Z   Z  EH  Z EH
4
E  Z   5
  0  4 Z EH  8Z EH  4ZEH  EH
Z  4
 5
  4Z   8Z   4Z   EH  0
 4
5
 4Z   4Z   0
4
5
 Z  Z 
16

So, the ground state energy,

E  2 Z 2 EH
2
 5
 2  Z   EH
 16 
2
 5
 2  Z   13.605 Other trial function yield values within 0.01% of the observed one.
 16 
 77.48 eV
Experimental  79.0 eV
Error  0.02 %

Recap
What we observed is that the perturbation method is failed to calculate the ground state energy of
Helium. The basic difficulty in solving the Schrödinger equation with this Hamiltonian stems
2
from the fact that the e
r12 is too large an effect to be treated as a perturbation. On the other
hand the variational principle is an effective approximation and is able to produce the
experimental observation.

Now the question is that,

“In this Helium problem can we use perturbation method?.”

The answer is : Yes, but we have to use “Central Field Approximation. In the next lecture, we
elaborate the central field approximation.
Lecture – 12 Central Field Approximation

In this lecture we will try to solve the problem of perturbation method while dealing with the
electron-electron coulomb repulsion for N-electron atoms.

We will also learn the symmetric and anti-symmetric wavefunction and exchange degeneracy for
identical particles.

We will know the method for incorporating Pauli exclusion for electron while evaluating the total
wavefunction of the multi-electron atom.

Next we will take some examples for calculating the energy levels of He-atom

Central Field Approximation:

 The basic difficulty in solving the Schrödinger equation stems from the fact that the
N
e2
interelectron repulsion 
i  j rij
is too larger an effect to be treated as a perturbation.

 It is that the inter electron repulsion contains a large spherically symmetric component. Thus it
is possible to construct a potential energy function U  ri  which is a spherically symmetric.
 One electron operator is a good approximation to the actual potential energy of the ith electron
in the field of the nucleus and the other N  1 electrons. The Hamiltonian may be written as,
H  H *  H1
2 N N
where H *  
2me
 i2  U  ri 
i 1 i 1

N
Z e2 N
e2
where U  ri   
i i 1 ri
 
i  j rij

e2
N N
e2
and H1     Non-Spherical part only
i  j rij i  j rij

N
e2
In which 
i  j rij
is the average over a sphere of the electron repulsion.

It is therefore independent of the angular coordinates, then H1 becomes the Hamiltonian which
contains the non spherical part of the electron repulsions, whereas H * contains the K.E, P.E in
the field of the nucleus, and the spherical average electron repulsion energy.
This is Known as central field approximation. The advantage of this approach is that, it is
assumed that H * contains most of the inter electron repulsion, the remaining term H1 is small
enough to be treated as a perturbation.
Since U  ri  is a one electron operator, the Schrödinger equation,

 2 N 2 N 
H *     i  U  ri     E
 2m i 1 i 1 

 is a product of single electron wave function i . When H * is allowed to operate on a product

wave function  , it operates on each of the i in turn, since the coordinates of each of electrons
are independently variable. So, the equation reduced to a set of N simultaneous equation, one
for each electron.
H1*1  E11 ; H 2*2  E22 ; ....
N
H *   H i* ; E   Ei
i 1 i

Each i is hydrogen type orbitals except radial part. These orbitals are called central field
orbitals.

Exchange Degeneracy and Identical particles

In the lecture-11, we have seen that in the independent particle model the wavefunction
  r1 , r2   a  r1  b  r2  is a solution of the Schrodinger equation
 2 2
Z e2 Z e2 
         r1 , r2   E   r1 , r2 
2 2
 1 2
 2m 2m r1 r2 

With the eigenvalue Ea  Eb

This Schrodinger equation is symmetrical, so a  r2  b  r1  is also a solution with the
same energy eigenvalue Ea  Eb
Here arises the degeneracy which is known as Exchange Degeneracy.
This is coming because of exchanging the two electrons

Now we take the linear combination of these

1
 S (r1 , r2 )  a  r1  b  r2   a  r2  b  r1 
2
and
1
 A (r1 , r2 )  a  r1  b  r2   a  r2  b  r1  
2
These are also the solutions of the same Schrodinger Equation with eigenvalue Ea  Eb .
 1
The factor is introduced to normalize the wavefunction.
2
The  S (r1 , r2 ) and  A (r1 , r2 ) are known as Symmetric and AntiSymmetric
wavefunctions.

The symmetric wavefunction  S (r1 , r2 ) remains same even we interchange the indices 1
and 2
On the other hand antisymmetric wavefunction  A (r1 , r2 ) changes sign if we interchange
indices 1 and 2.
This is required because of the indistinguishability of identical particles like electrons.
In Classical mechanics, identical particles are distinguishable, because it is possible to
define the individual particles in terms of their space coordinate and time.
However, in Quantum mechanics, this is not possible. So, identical particles are always
considered to be indistinguishable.

For two electrons system, when the two electrons are interchanged, then the
wavefunctions are related with a phase factor as
(r1 , r2 )  ei (r2 , r1 ) where  is a real constant.
Now, we define P12 as the particle interchange operator.
P12 (r1 , r2 ) (r2 , r1 ) So P122 (r1 , r2 )  P12 (r2 , r1 ) (r1 , r2 )
Again, P122 (r1 , r2 )  P12 (r2 , r1 )  ei P12(r1 , r2 )  ei (r2 , r1 )  e2i (r1 , r2 )

P122 (r1 , r2 )  e2i (r1 , r2 ) Thus, e2i  1 So ei  1 and thus, (r1 , r2 )   (r2 , r1 )

The “+” sign is for symmetric state and “-“ sign is for antisymmetric state.
This shows that the wavefunction should be either symmetric or antisymmetric with respect to the
interchange of the electrons.
If the two electrons are in the symmetric or antisymmetric state in a system, then these electrons
remain in that state for all time unless it disturbed by external perturbation.
The Pauli Exclusion Principle
So far we discuss about the space part. For a full description of the total system, we have to
consider the spin of the electrons also.
We define,  as the spin up i.e. spin s = ½ , and ms = +½
And  as the spin down i.e. spin s = ½ , and ms = -½
For two electron system we have to take again the linear combination of these spin states.
Because of the indistinguishability of the electrons, we have to construct the linear combination
in the symmetric and antisymmetric manner with respect to the interchange of the indices of the
electrons.
 S   (1) (2)
  (1)  (2)
Symmetric : 1
  (1) (2)   (2)  (1)
2

1
Antisymmetric  A   (1) (2)   (2) (1)
2

In this, the symmetric state contains three wavefunctions and antisymmetric contains one
wavefunction.
According to the Pauli Exclusion principle, “No two electrons will have the same quantum
numbers (n, l, ml, s, ms).
It means that “the wavefuntion for a system of electrons must be antisymmetric with respect to the
interchange of the electrons”

So for two electron system, the total wavefunction would be antisymmetric when we multiply the
symmetric space wavefunction with antisymmetric spin wavefunction
  S (r1 , r2 )  A
And when we multiply the antisymmetric space wavefunction with symmetric spin wavefunction
   A (r1 , r2 )  S
For a system with N electrons, the antisymmetric total wavefunction is given by the Slater
determinant

 1  1   2  1  ..  N  1 
 1  2   2  2  ..  N  2 
1
  1 , 2 ,...., N   .. .. .. ..
N!
.. .. .. ..
 1  N   2  N  ..  N  N 

Where  n m ms  n m  r    ms  ;
when two would become same, determinant would vanish.
Hartree’s method of Self Consistent field for N-electron system
The best single electron atomic wave functions are the self consistent field (SCF)
functions introduced by Hartree (1927).
To obtain these, we start with a set of N approximate single electron functions. Using of
these except the ith function, the average field due to their charge clouds is calculated.
This constitutes the potential field in which the ith electron moves. Solution of the ith
equation gives an improved wave function J .
This is repeated for each of the N electrons, giving first improved, single electron wave
functions.
These are then used to calculate a set of second improved wave functions, and so on; the
process is continued until no further improvement is registered.
In other words, the electrons are supposed to move in a potential which they themselves
generate. This is the reason it is known as Self Consistent
The calculated energy of the atom is the sum of the energies Ei of the individual
electrons, minus the coulomb repulsion energy averaged over all pairs of electron wave functions,
since this gets included twice over for each pair of electrons i & j , once in calculation Ei and
once in E j . The energy of each of the SCF/AO’s, is found to be a function of n and .

When the central field orbital is multiplied by a spin function   ms  which is  or  ,

we have a one-electron, central field spin orbital.
n m ms  n m  r    ms  Characterized by the four quantum nos. n, , m , ms .
Finally the spin orbitals may be organized into an antisymmetric N -electron wavefunction in
order to satisfy the requirements of the Pauli principle.
 1  1   2  1  ..  N  1 
 1  2   2  2  ..  N  2 
1
  1 , 2 ,...., N   .. .. .. ..
N!
.. .. .. ..
 1  N   2  N  ..  N  N 

in which  i  i  are spin orbitals.

The distribution of electrons with n and are known as configuration. Electrons in orbitals with
same n and are said to be equivalent.
 2
Z e2 Z e2 e2
Example: He atom Hamiltonian H  
2me

2
1  22  
r1

r2

r12
2
In zeroth order approximation; ignore e term.
r12
2
Z e2 2
Z e2
H 
0
  2
1 2 
2

So, 2me r1 2me r2

 H1  H 2
Eigen functions of H 0 ,  1, 2   a 1 b  2 
This is the product wavefunction with the electron coordinates replaced by 1 & 2 .
Eigen values, E0  Ea  Eb
Next part is to introduce the inter electronic repulsion term as a perturbation.
e2
Eee    1, 2   1, 2  d
r12
e2
  a 1 b  2  a 1 b  2  d
r12

So the total Energy of the system E   Ea  Eb   Eee

Ground state of Helium :

In zeroth order approximation, the ground state of helium is therefore represented by

1s 1 1s  2  , where 1s is hydrogen like wavefunction

Wavefunction  1, 2  1s 1 1s  2   Symmetric 

Multiply it by antisymmetric spin function to make the total wavefunction antisymmetric.
 1, 2   1, 2   A
So the unperturbed energy E0  E1s  E1s
e2
Eee    1, 2   1, 2  d
r12
First order perturbation energy
e2
  1s 1 1s  2  1s 1 1s  2  d
r12

So, the ground state energy E  E1s  E1s  Eee

This will give slight shift from unperturbed energy level  E0  , which will be same as Central
field approximation energy levels.
Excited states of Helium :

For excited states,  should be linear combinations of a 1 b  2  & a  2  b 1 .

1
 S (r1 , r2 )  a  r1  b  r2   a  r2  b  r1 
2

1
 A (r1 , r2 )  a  r1  b  r2   a  r2  b  r1  
2

First order interelectron repulsion perturbation,

e2
Hss    s  s d  C1  A1
r12
e2
Haa    a  a d  C1  A1
r12
e2
where, C1   a 1 b  2  a 1 b  2 
r12
e2
A1   a 1 b  2  a  2  b 1
r12

C1 represents the Coulombic Interaction of the electron charge clouds a2 1 & b2  2  .
A1 is called Exchange Integral.
Next is to include spin to get spin orbital. So,
1 1
Singlet a 1 b  2   a  2  b 1   1   2    1   2  
2 2
1
Triplet a 1 b  2   a  2  b 1   1   2 
2
1
a 1 b  2   a  2  b 1   1   2 
2
1 1
a 1 b  2   a  2  b 1   1   2    1   2  
2 2
First excited state :
Case: 2 1s 2s
1s 1 2 s  2 
product wavefunction
2 s 1 1s 1
 1
Symmetric wavefunction  S 1, 2   1s 1 2 s  2   2 s 1 1s  2  
2
1
And the antisymmetric wavefunction  A 1, 2   1s 1 2 s  2   2 s 1 1s  2  
2
We have to multiply it with corresponding symmetric and antisymmetric spin wavefunction.

First order energy

e2
E1ees,2 s ( Singlet )    s 1, 2   s 1, 2  d
r12
2

1
1s 1 2 s  2   2 s 1 1s  2  re 1 1s 12 s  2   2 s 11s  2  d
2 12 2
1 e2 1 e2
 2 1s 1 2 s  2  1s 1 2 s  2  d  2  1s 1 2 s  2  2 s 1 1s  2  d
2 r12 2 r12
 C1s ,2 s  A1s ,2 s
E1ees,2 s (triplet )  C1s ,2 s  A1s ,2 s A1 exchange integrals
The spin wavefunctions are normalized and integrations give values 1

A1 Siglet

A1 Triplet
C1

Independent Term
Particle Model

So the energy difference: 2A1

Note that
1) For closed shell, such as 1s 2 , this exchange integral is not present. So there is no splitting.
Even for other closed shell, the exchange integral is present.
2) For closed shell i.e. both coulomb and exchange potential are spherically symmetric.
3) For all excited states of Helium, the energy levels split into two, Singlet and Triplet
4) Splitting comes from exchange integrals so this is non central part of the electrostatic
repulsion.
5) Before that it is just central field approximation
The Helium atom energy levels

E1s,3p

E1s,3s

E1s,2p

E1s,2s

E1s,1s
Singlet (C+A) Triplet (C-A)
Independent
particle model Including electron-electron repulsion

Recap
Here we discussed the method for handling the large coulomb repulsion part in the
perturbation method.

The saving feature of the problem is that the large part of the electron repulsion contains
a large spherically symmetric component.

This spherically symmetric part can be treated with one electron operator and is a good
approximation to make a potential of ith electron in the field of nucleus and (N-1)
electrons.

The asymmetric part causes the splitting of energy levels and for helium this produces
singlet and triplet states. The splitting energy is the value of the exchange integrals.
Lecture - 13 Coupling of angular momentum

In this lecture we will go through the method of coupling of angular momentum.

We will start with the need for this coupling and then develop the method for evaluating
coupled state in terms of uncoupled states.

First we will take up the case of coupling of two generalized angular momenta and then
utilize this to take the case of three angular momenta.

In previous lecture, we have seen that the electron-electron repulsion term is responsible
for the splitting of energy levels. The reason for this is the one electron quantum numbers
are not the good quantum numbers for the total Hamiltonian.
 e2 
Because, H1    does not commute with , but H1 commutes with L and S where
r  i
 ij 
L i ; S   Si . It is equivalent to saying that H1 is invariant under a rotation of
i i

spatial and spin coordinates.

Proof:
1 1
 H1 , L  e2  k  e2  k
i j k rij i  j rij rij
where, k  irk  k

Allowing the operators to act on arbitrary function 

 1  1 1
 k    k   
  r  r k
rij 
 ij  ij
 
 1  1 1 
 k    k  k 
  rij  rij rij 
1 1 
  i rk   k  
rij
k r
 ij 

1 1
So  H1 , L   e2  k  e2  k
i j k rij i j k rij
1 1 1 
 e2   e2   i e2  rk   k  
rij
k
rij
k r
i j k i j k i j k  ij 
 1   ri  rj ri  rj 
Now, r k k      rk  3  ik  rk  3  jk 
k  rij  k  rij rij 
ri  rj ri  rj
 3  3 0
rij rij
So  H , L   0
Similarly  H , S   0

The angular momentum for an atomic electron can be visualized in terms of a vector
model where the angular momentum vector is seen as precessing about a direction in
space.

Let us consider the set of states having a common value of the quantum number j. For
each of these states the length of the orbital angular momentum vector,  j ( j  1) in
units of .

The z-component of this vector is m in units of .

For example if j = 2 then there are five projections as shown in the figure.

Z
2 2(2  1)

-1

-2
In this model, we can understand that, for two electron system, the electron-electron
repulsion is responsible to couple l1 and l2 to form the resultant vector L .Similarly, s1 and
s2 to form the resultant vector S

l1 s2
l2

s1
Generalized angular momentum operator J is defined as a vector operator with
Hermitian components J x , J y and J z satisfying J  J  iJ

The components are defined as

J  
1
2
 J x  iJ y  , J 0  J z and J 
1
2
 J x  iJ y 
And the inverse relations are

1 1
Jx    J   J   and J y   J   J  
2 2

The commutation relations between them are

 J0 , J    J  ,  J0 , J    J , and  J  , J     J 0

Since J x , J y and J z are Hermitian, the total angular momentum operator

J 2  J x2  J y2  J z2   J  J   J 02  J  J 

Using the Dirac notation, the eigen functions are represented as j, m where m is the
projection of J, we have

J 2 | j m  j  j  1 | J m
J z | j m  m | j m
j m jm   jj mm

Similarly we have

1
J  j, m    j ( j  1)  m(m  1) j, m  1
2

And

1
J  j, m   j ( j  1)  m(m  1) j, m  1
2
Coupling of Angular Momenta

Two angular momentum operators J1 and J 2 operate on two different spaces

| j1 , m1  and | j2 , m2  such that,

J12 | j1 m1   j1  j1  1 | j1 m1  

J1z | j1 m1   m1 | j1 m1  
     1
J 2 | j2 m2   j2  j2  1 | j2 m2  
2

J 2 z | j2 m2   m2 | j2 m2  


Let us define,
  
J  J1  J 2

J x  J1x  J 2 x 

With understanding J y  J1 y  J 2 y       2 

J z  J1z  J 2 z 

J t  J x  iJ y
  J1 x  J 2 x   i  J 1 y  J 2 y 
And
  J1x  iJ1 y    J 2 x  iJ 2 y 
 J t  J1t  J 2t

Now the question is whether J will be an angular momentum?

For this it should follow all the commutation relation for generalized angular
momentum.

 J x , J y    J1x  J 2 x , J1 y  J 2 y 
  J1x , J1 y    J1x , J 2 y    J 2 x , J1 y    J 2 x , J 2 y 
( for different spaces )
  J1x , J1 y    J 2 x , J 2 y 
 iJ1z  iJ 2 z  i  J1z  iJ 2 z   iJ z

So,  J x , J y   iJ z
The other relations will also follow. So we can conclude that

J  J  iJ

And this relation is sufficient to identify J as an angular momentum operator.

So the orthonormal Eigen function corresponding to this operator is:

| j1 , j2 , j , m  | j , m

The meaning of this notation is that, the coupled | j m should arise from two uncoupled
Eigen function | j1 m1  and | j2 m2  .

J 2 | j m  j  j  1 | j1 j2 j m
So,
J z | j m  m | j1 j2 j m

1 3
Where, j  0, ,1, ,.........
2 2

and m  j, j  1, j  2,.........,  j  2 J  1 values

Now we have to setup the relationships between coupled Eigen function | j m and
uncoupled Eigen functions | j1 m1  and | j2 m2  .

Similarly, coupled Eigen values j , m with uncoupled Eigen values j1 , j2 and m1 , m2 .

Let us construct a product wavefunction,

| j1 j2 m1 m2   | j1 m1  | j2 m2 

As we know that, the products and their linear combinations are also the Eigen functions
of J12 , J1z and J 2 2 , J 2 z .

J12 | j1 j2 m1 m2   J12 | j1 m1  | j2 m2   j1  j1  1 | j1 m1  | j2 m2   j1  j1  1 | j1 j2 m1 m2 
J 2 2 | j1 j2 m1 m2   J 2 2 | j2 m2  | j1 m1   j2  j2  1 | j1 m1  | j2 m2   j2  j2  1 | j1 j2 m1 m2 
J1z | j1 j2 m1 m2   J1z | j1 m1  | j2 m2   m1 | j1 m1  | j2 m2   m1 | j1 j2 m1 m2 
J 2 z | j1 j2 m1 m2   J 2 z | j2 m2  | j1 m1   m2 | j1 m1  | j2 m2   m2 | j1 j2 m1 m2 
Now, let us apply J z on the uncoupled Eigen functions:

J z | j1 j2 m1 m2    J1z  J 2 z  | j1 j2 m1 m2 
 J1z | j1 m1  | j2 m2   J 2 z | j2 m2  | j1 m1 
  m1  m2  | j1 m1  | j2 m2 
 m | j1 m1  | j2 m2 

If m  m1  m2 , then | j1 j2 m1 m2  is an Eigen function of J z .

Since J 2   J1  J 2   J12  J 22  2 J1 J 2
2

| j1 j2 m1 m2  will not be the Eigen function of J 2 .

So, we have to find a common Eigen function of J 2 and J z .

We construct a linear combination of the uncoupled Eigen function, such that

| j1 j2 j m   j
m1 , m2
1 j2 m1 m2 | j1 j2 j m | j1 j2 m1 m2 
Eigen functionof Numeric value known as Eigen functionof
J 2 and J z Vector AdditionCoefficients J1 and J 2
or ,
Clebsch GordonCoefficients

We have to find out the relationships between the quantum numbers representing the
coupled and uncoupled Eigen functions.

First applying J z on both sides of the equation, we get:

m | j1 j2 j m   m  m   j
m1 , m2
1 2 1 j2 m1 m2 | j1 j2 j m | j1 j2 m1 m2 

It suggests that the value of  j1 j2 m1 m2 | j1 j2 j m  0 if m  m1  m2

We have to find the possible values of j

We know that

 j1  m1  j1 and  j2  m2  j2

Since m  m1  m2

We have  j1  m  m2  j1 and  j2  m  m1  j2
Let m assume its maximum value j, m1 its maximum value j1

and m2 its maximum value j2 then

 j1  j  j2  j1 and  j2  j  j1  j2

So j2  j1  j  j1  j2 and j1  j2  j  j1  j2

Combining these two we get j1  j2  j  j1  j2

1 1 1
For example if, j1  , m1  ,  and j2  1, m2  1,0, 1 , then the possible values of
2 2 2
1 1 1 3 3 1 1 3
j  , m   ,  and j  , m   ,  ,  , 
2 2 2 2 2 2 2 2

because

m  m1  m2
1 3 1 1
  1   ,   1  
2 2 2 2
1 1 1 1
  0  ,   0 
2 2 2 2
1 1 1 3
  1   ,   1  
2 2 2 2

It is also important to put the condition that j1  j2  j  n , where n is an integer.

This follows that

j1  j2  j 

j1  j2  j   0 . This is known as triangular conditions.
 j1  j2  j 

Considering all these we have, j  j1  j2 , j1  j2  1, j1  j2  2,........., j1  j2

And m  j, j 1,..........,  j

Coupling of three angular momenta

Let take three angular momenta J1, J2 and J3 such that J  J1  J 2  J 3

1 1
There are three ways to couple these. As an example, j1  , j2  , j3  1
2 2
 1 1
Case -1, First couple j1  and j2 
2 2

1 1
 2 , 2  0
This gives j1 , j2  j12  
 1 , 1 1
 2 2

Now we couple j12 with j3  1

 1 1 
  2 , 2   0 ,1  1
 
 1 1 
  ,   1 ,1  0
 2 2 
This gives j  j1 , j2 ( j12 ), j3  j12 , j3  
  1 , 1   1 ,1  1
  2 2 

 1 , 1   1 ,1  2
 2 2   

1
Case-2 First couple j1  and j3  1
2

1 1
 2 ,1  2
This gives j1 , j3  j13  
 1 ,1  3
 2 2

1
Now we couple j13 with j2 
2

 1   1  1
  2 ,1   2  , 2  0
   
 1  1  1
  ,1    ,  1
2  2 2
This gives j  j1 , j3 ( j13 ), j2  j13 , j2  
  1 ,1   3  , 1  1
  2   2  2

 1 ,1   3  , 1  2
 2   2  2
 1
Case -3 First couple j2  and j3  1
2

1 1
 2 ,1  2
This gives j2 , j3  j23  
 1 ,1  3
 2 2

1
Now we couple j23 with j1 
2

 1   1  1
  2 ,1   2  , 2  0
   
 1  1  1
  ,1    ,  1
2  2 2
This gives j  j2 , j3 ( j23 ), j1  j23 , j1  
  1 ,1   3  , 1  1
  2   2  2

 1 ,1   3  , 1  2
 2   2  2

Note: When three angular momentum operators are coupled to form the total angular
momentum, the possible values of the total angular momentum will be the same,
independent of the method of coupling scheme. However, the coupled wavefunctions
(discussed later) will depend on the coupling scheme.

Recap
In this lecture, we have learnt that the two angular momenta get coupled to form new
angular momentum.

The reason for coupling of angular momentum is to form a new basis set that will be the
eigenfunction of the total Hamiltonian.

In case of three angular momenta, the coupled angular momentum does not depend on
the coupling scheme. However, the coupled wavefunction arising from the uncoupled
state does depend on the coupling scheme.

We will understand this in the next lectures.

Lecture – 14 Evaluation of Terms of an atom
In this lecture, we will learn the method to evaluate the spectroscopic terms arising from
the electronic configuration of an atom.

The terms of an atom are the energy levels evaluated by considering the electron-electron
repulsion in the Hamiltonian.

In previous lectures, we have understood that the electronic wavefunctions in the central
field approximation are characterized by four basic single electron quantum numbers :
n, l , ml , ms

These are the good quantum numbers with respect to the Central field Hamiltonian

 2 N 2 N 
H *     i  U  ri     E
 2m i 1 i 1 

The reason is

H1*1  E11 ; H 2*2  E22 ; ....

N
H *   H i* ; E   Ei
i 1 i

e2
When non-spherical part of the electron-electron repulsion  r is included in the
ij

Hamiltonian , these single electron quantum numbers are no more the good quantum
numbers since they do not commute with the Hamiltonian
2
Z e2 Z e2 e2
H 
2me
12  22   r1

r2

r12

In this case  H , L  0 H , S   0
And also  H , L2   0  H , S 2   0

Where L  l1  l2  l3  ....   li , similarly S  s1  s2  s3  ....   si

So, L and S are the good quantum numbers to characterize the total wavefunction of the
system. In this regard we have discussed in the last lecture about procedure and rules of
the coupling of angular momenta.
The energy levels will be in terms of L and S and are thus named as Terms. The notataion
2 S 1
for these terms are L and coupled wavefunctions are L, S , M L , M S

Next we will use the coupling of angular momentum procedure to find out the terms
arising for a multielectronic atom from its electronic configuration.

Now let us understand the degeneracy of a level arising from the electronic configuration.

The distribution of electrons with n and are known as configuration.

Example: For Helium : electronic configuaration of the ground state is 1s 2
For Carbon: 1s 2 2s 2 2 p 2
Electrons in orbitals with same n and are said to be equivalent.
Electrons in orbitals with different n or are said to be nonequivalent
Such as Excited state of Helium: 1s1 2s1 or 1s1 2 p1 e.t.c

The case of a sub shell (same n and ) degeneracy,

 0  s  max. no. of electrons  2
2  2  1 2  1 for m 1  p max. no. of electrons  6
2s  1 for ms 2 d  max. no. of electrons  10
3 f max. no. of electrons  14

A sub shell containing 2  2  1 electrons is said to be complete.

Order of degeneracy of a configuration:

1) A single electron in each subshell.

Yi  2  2 i  1
So degeneracy G   Yi
i

1s 2s 2 p G  2  2  6  24
Ex.
2 p 3d 4 f G  6 10 14  840

2. Several electrons in the same subshell.

Y!
degenaracy of a shell g 
X !Y  X !
X  no of electrons; Y  total no of electrons occypyin that shell
 Example:
What is the degeneracy G of the ground state of carbon (6)?
Configuration 1s 2 2s 2 2 p 2
For 1s X  2 ; Y  2 , g  1
For 2s X  2 ; Y  2 , g  1 G  15
For 2 p X  2 ; Y  6 , g  15

Example
1s 2 2s 2 2 p 2 3 p1 excited state of Nitrogen
1s g 1
2s g 1 G  15  6  90
2 p2 g  15
3p X 1 Y  6 g  6

Now, we will find out the terms using the rules for the coupling of angular momenta are

L  l1  l2 , l1  l2  1,..........., l1  l2

S  s1  s2 , s1  s2  1,..........., s1  s2 M L  ml1  ml2 M s  ms1  ms2

Case of Helium: Distribution of electrons with n and are known as configuration.

electronic configuaration of the ground state is 1s 2

1s 2 ; 1 0 ; 2 0 ; L0
s1  1 ; s2  1
; S  1 and 0;
2 2
So the terms are 1S and 3S , but 3S will not be there because it violates the Pauli
exclusion principle.
Excited states:
1s1 2s1 ; 1 0 ; 2 0 ; L0
So the terms are 1S and 3S .
s1  1 ; s2  1 ; S  1 and 0;
2 2

1s1 2 p1 ; 1 0 ; 2 1 ; L 1
So the terms are 1P and 3 P
s1  1 ; s2  1 ; S  1 and 0;
2 2

1s1 2d 1 ; 1 0 ; 2 2 ; L2
So the terms are 1D and 3 D .
s1  1 ; s2  1 ; S  1 and 0;
2 2
Example: Carbon:

Ground electronic configuration 1s 2 2s 2 2 p 2

2 p2 ; 1 1 ; 2 1 ; L  2, 1, 0
terms are 3D, 1D, 3P, 1P, 3S , 1S ,
s1  1 ; s2  1 ; S  1 and 0;
2 2

however only 1D, 3P, 1S will survive because of the Pauli exclusion principle.

Excited states :

Configuration : 2 p1 3s1

2 p13s1 ; 1 1 ; 2 0 ; L 1
So the terms are 3 P, 1P
s1  1 ; s2  1 ; S  1 and 0;
2 2

Configuration : 2 p1 3 p1

2 p13 p1 ; 1 1 ; 2 1 ; L  2, 1, 0
terms are 3D, 1D, 3P, 1P, 3S , 1S
s1  1 ; s2  1 ; S  1 and 0;
2 2

This is the way terms are evaluated from the electronic configuration. We have also seen
for two equivalent electrons, only terms survive with L  S  even . For three electrons
there are no straight forward rules for that. To evaluate the terms, thus we follow the
M L  M S table. This is most general method and provides insight of the each electron
quantum numbers to evaluate the terms.

Construction of ML  MS Table

1. First find out the ML from ml1 and ml2 and MS from ms1 and ms2

2. Use the notation to make a table. ml1 s1 , ml2  m ms2

.
3. For filling up, we have to keep in mind the coupling rules
M L  ml1  ml2 M s  ms1  ms2

4. We have to also remember the Pauli exclusion principle i.e. not two electrons
have the same quantum numbers n, l , ml , s, ms
Example.

Configuration : 1s 2 (equivalent electrons) and 1s 2s nonequivalent electrons

1s 2 /1s 2s ; 1  0 ; ml1  0 2  0 ; ml1  0

L  0, M L  0

s1  1 ; ms1  1 ,  1 s2  1 ; ms2  1 ,  1
2 2 2 2 2 2
S  1 and 0; M s  1, 0, 1

ml ms Notation

0 1 0
2
0
1 0
2

Now make the M L  M S

For 1s 2
MS \ ML 0

1 0 0

0 0 0
0 0

-1 0 0

Here, the crossed terms will not survive because of the Pauli Exclusion principle. Now
for finding the terms, start with highest ML = 0 and highest Ms = 0. This will arise from L
= 0 and S = 0. The degeneracy is 1. So the terms is 1S
For 1s 2s
MS \ ML 0

1 0 0

0 0 0
0 0

-1 0 0

Here, the all terms will survive. Now for finding the terms, start with highest ML = 0 and
highest Ms = 1. This will arise from L = 0 and S = 1.

The degeneracy (2L+1)(2S+1) is 3. There will be three combinations coming from each
block corresponding to the terms is 3S .

There will be one combination in ML = 0 and Ms = 0. The terms is 1S

So the terms arising from 1s 2s are 3S and 1S

Another example. p2 Degeneracy of this configuration is 15

1  1 ; m 1  1, 0, 1 s1  1 ; ms1  1 ,  1
2 2
2 1 ; m 2
 1, 0, 1 s2  1 ; ms2  1 ,  1
2 2

L(max)  2, M L  2,1,0, 1, 2 S (max)  1, M s  1,0, 1

MS \ ML 2 1 0 -1 -2
1 0 0 0 1 0
1
1  1
1 1 1 0 0 0 1 0 1  1
0 1 0 1  1 1 0
1  1
1 0 0 0 1 0
-1
1  1
L2 M L  2,1, 0, 1, 2 1
 D  5 levels
S 0 MS  0 
Remove one combination from each block of ML and MS .

L 1 M L  1, 0, 1 3
 P  9 levels
S 1 M S  1, 0, 1
ML 1 1 1 0 0 0 1 1 1
MS 1 0 1 1 0 1 1 0 1

Remove one combination from each block of ML and MS

L0 M L  0 1
 S 1
S 0 M S  0

Remove one combination from each block of ML and MS

Total  15 levels

Note that p4 will also have the same terms.

Now p p configuration : Degeneracy of this configuration

2  1 2  1 2s  1 2s  1

3  3  2  2  36

MS \ ML 2 1 0 -1 -2
1 1 1 0 1  1 1 0 1  1
1 0 1 1 1 0  1
0 0
1 1 1 0  1  1 1 0 1  1
1 1 1 0  1  1 1 0 1  1
0  1 1 1 0  1
0
0  1 1 1 0  1
0 0
0 0
1 1 1 0 1  1 1 0 1  1
-1 0 1 1 1 0  1
0 0
L2 M L  2,1, 0, 1, 2
  15 levels
S 1 M S  1, 0, 1 

L2 M L  2,1, 0, 1, 2

  5 levels
S 0 MS  0 

L 1 M L  1, 0, 1
  9 levels
S 1 M S  1, 0, 1

L 1 M L  1, 0, 1
  3 levels
S 0 MS  0 

L0 ML  0 
  3 levels
S 1 M S  1, 0, 1

L0 M L  0
  1 level
S 0 M S  0

Total  36 levels

Now we calculate the energies for the splitting

For two electrons semi-empirical

E  L M L S M S a1 1 2  a2 s1  s2 S M S L M L

a1 & a2 function of n, .i.e. a1  n,  ; a2  n, 

L 1 2

L2  12  22 2 1 2
2
L  1 2
2 2
 1 2 
2

L2  2
 2
1
L ML 1 2
L ML   L  L  1    2
1 1  1 
2
1 2
2

S 2  s12  s22 1
S MS S M S   S  S  1  s1  s1  1  s2  s2  1
2 2
 a1 a2
E   L  L  1   1 1  2  1   S  S  1  s1  s1  1  s2  s2  1
2 2 
1 2

1s 2 ; S , L  0 ; 1 0 ; s1  1
2
S 0 ; 2 0 ; s2  1
2

a1  1  1  1  1 
a
E   0  2
0  2  2  1  2  2  1 
2  2    
a  3 3 3
 2       a2
2  4 4 4

The energy E is positive so a2 is negative

1
S
3
a2
4
Configuration s2
Terms

1s 2s

1
S L0; S 0; 1  0, 2  0 ; s1  1 , s2  1
2 2
3
S  L  0 ; S 1 ; 1  0, 2  0 ; s1  1 , s2  1
2 2

a1 a
0  2 0   
3 3
1
S : E 
2 2  4 4
3
  a2
4
a a   3
3
S : E  1  0  2  2  
2 2  2
a2

4

The constant a2 is negative.

1
S 3
a2
4
Configuration s2 1 
a
Terms
3
S 4 2
1s 2 p

1
P  L 1 ; S 1 ; 1  1, 2  0 ; s1  1 , s2  1
2 2
3
P  L 1 ; S 1 ; 1  1, 2  0 ; s1  1 , s2  1
2 2

a1 a 
 2  2  2 0  
3
1
P : E 
2 2  2
3
  a2 1
4 P 3
a2
a  4
3
P : E  2
4 Configuration s2 1 
a
3
Terms P4 2

Now let us look at the terms arising from three electrons configuration p3

 1 ; m 1  1, 0, 1 s1  1 ; ms1  1 ,  1
1 2 2
2 1 ; m  1, 0, 1 . s2  1 ; ms2  1 , 1
2 2 2
3  1 ; m 3  1, 0, 1 s3  1 ; ms3  1 , 1
2 2

L(max)  3, M L  3, 2,1,0, 1, 2, 3 S (max)  3 , M s  3 , 1 ,  1 ,  3

2 2 2 2 2

MS \ ML 3 2 1 0 -1 -2 -3
3 1 0  1
2
1 0 0 1 0  1 1  1  1 1 0  1
1 0 1 1  1 1 1  1 0 0  1 0
0  1 1
1
2
1 0 1 1 1  1 1 0  1 1 0  1 1 0  1
0 1 0 0 1  1 0  1 0
1
2
1 1 0
3 1 0  1
2
Let us write down the number of combination in each block

MS \ ML 2 1 0 -1 -2
3 1
2

1 1 2 3 2 1
2

1 2 3 2 1
1
2
3
2 1
Terms arising from maximum ML = 2 and maximum MS = 1/2 is 2 D . Total combination
for this term is 10. Take out from each block of ML = 2,1,0,-1,-2 and MS = ½ and -½ .

That reduces to

MS \ ML 2 1 0 -1 -2
3 1
2

1 0 1 2 1 0
2

0 1 2 1 0
1
2
3
2 1
Next Terms arising from maximum ML = 1 and maximum MS = 1/2 is 2 P . Total
combination for this term is 6. Take out from each block of ML = 1,0,-1, MS = ½ and -½ .

MS \ ML 2 1 0 -1 -2
3 1
2

1 0 0 1 0 0
2

0 0 1 0 0
1
2
3
2 1
Next Terms arising from maximum ML = 0 and maximum MS = 3/2 is 4 S . Total
combination for this term is 4. Take out from each block of ML = 0 MS =
3 , 1 , 1 , 3 , .
2 2 2 2

-15

Helium Spectroscopic Terms

Spectroscopic terms of Equivalent electrons and their degeneracy

Electronic Configuration Number of Spectroscopic Terms

degenaracy

ns1 1 2
S

ns 2 1 1
S

np0 , np6 1 1
S

np, np5 6 2
P

np 2 , np 4 15 1
S , 1D, 3P

np 3 20 2
P, 2 D, 4S

nd 0 , nd 10 1 1
S

nd , nd 9 10 2
D

nd 2 , nd 8 45 1
S , 1D, 1G, 3P, 3F

nd 3 , nd 7 120 2
D(2), 2 P, 2 F , 2G, 2 H , 4 P 4 F

nd 4 , nd 6 210 1
S (2), 1D(2), 1F , 1G(2), 1I , 3P(2),
3
D, 3 F (2), 3G, 3H , 5 D

nd 5 252 2
S , 2 P, 2 D(3), 2 F (2), 2G(2), 2 H , 2 I , 4 P,
4
D, 4 F , 4G, 6 S

nf , nf 13 14 2
F

Here we have learnt the evaluation of the spectroscopic terms arising from the electronic
configuration of an atom

This way we can evaluate the terms of an atom for the ground an excited states.

We also can calculate the shift of energies of the terms using semi-empirical method.
Lecture – 15 Evaluation of coupled wavefunction
In this lecture we will the procedure for evaluating the coupled wavefunctions in terms of
the uncoupled states.

Initially, we will start with coupling of two generalized angular momenta.

Since the total wavefunction for the electron is the product of the space and spin
wavefunction, we will learn how to make the total wavefunction antisymmetric.

As mentioned in the previous lectures that for three angular momenta coupling, the final
wavefunctions depend on the detailed coupling scheme, we will find the proof.

In previous lecture we learnt that when non-spherical part of the electron-electron

e2
repulsion  is included in the Hamiltonian , these single electron quantum numbers
rij
are no more the good quantum numbers since they do not commute with the Hamiltonian
2
Z e2 Z e2 e2
H 
2me
2
1  22  
r1

r2

r12

In this case  H , L  0 H , S   0
And also  H , L2   0  H , S 2   0

Where L  l1  l2  l3  ....   li , similarly S  s1  s2  s3  ....   si

So, L and S are the good quantum numbers to characterize the total wavefunction of the
system. In this regard we have discussed in the last lecture about procedure and rules of
the coupling of angular momenta.

The energy levels will be in terms of L and S and are thus named as Terms. The notataion
for these terms are 2 S 1L and coupled wavefunctions are L, S , M L , M S

We can evaluate the coupled wavefunction L, S , M L , M S in terms of uncoupled basis

sets l1 ml1 l2 ml2 and s1 ms1 s2 ms2

Here we will learn this method.

We have understood in lecture-13 about the coupling of angular momenta. The

uncoupled wavefunctions are j1 m1 and j2 m2 . The J12 , J 22 and J1z , J 2 z when operate on
these eigenfunctions provide
J12 | j1 m1   j1  j1  1 | j1 m1  

J1z | j1 m1   m1 | j1 m1  

J 2 | j2 m2   j2  j2  1 | j2 m2  
2

J 2 z | j2 m2   m2 | j2 m2  


1
Also we know that J J , m   J ( J  1)  m(m  1) J , m  1
2

The coupled wavefunction J , m is related to uncoupled wavefunctions j1 m1 and

j2 m2 as

| j1 j2 J m   j
m1 , m2
1 j2 m1 m2 | j1 j2 J m | j1 j2 m1 m2 
Eigen function of Numeric value known as Eigen function of
J 2 and J z Vector AdditionCoefficients J1 and J 2
or ,
Clebsch GordonCoefficients

 j j J 
 (1) j2  j1  m  2J 1  1 2  j1 j2 m1 m2
m1 , m2  m1 m2 m 

 j j J 
With restriction m  m1  m2 . Here  1 2  is known as 3j symbol. Using this
 m1 m2 m 
relation, one can calculate the coupled wavefunction by knowing the value of 3j.

However, there is a simple method to calculate the coupled wavefunction. In the

following we discuss this method.

The method is

1. First find out the maximum J from j1 and j2.

2. Write down the wavefunction J max , mmax  j1max , m1max j2max , m2max . The
coefficient will be one because there will be only one term ( m  m1  m2 ) and the
uncoupled wavefunctions are normalized.

3. Then operate J  on J max , mmax to obtain J max , mmax  1

4. Then write J max  1, mmax  1 in terms of j1 m1 and j2 m2 using all possible

combination keeping in mind m  m1  m2 .
 5. Use orthogonal and orthonormal properties to find out the coefficients of these.

The figure below illustrates this method.

Orthogonal and
Orthonormal
properties

m
(3,3)
J
(2,2)
(3,2)
J
(1,1)
(3,1)
(2,1)
J

(0,0) (1,0) (2,0) J

Let us work out some examples.

1 1 1 1 1 1
j1  ; j2  m1  ,  ; m2  , 
2 2 2 2 2 2

j1 j2 m1 m2  j1 m1 j2 m2
1 1 1 1

2 2 2 2

J  j1  j2 to j1  j2
1 , 0
 J m  11 

J 1 ; m  1, 0, 1 ; 10 
1 1 

J 0; m0 ; J m  0 0 

m  m1  m2

j1,m1 j2,m2
J ,m
1 1 1 1
11 
2 2 2 2

Operate both sides J  to get 1, 0

J  1 1  11  1  11  1 1 0
 2 10
1 1 1 1 1 1 1 1 1 1 1 1
J  J1  J 2
2 2 2 2 2 2 2 2 2 2 2 2
11 1 11 1 1 1 1 1 11 1 11 1 1 1 1 1

              
22 2 22 2 2 2 2 2 22 2 22 2 2 2 2 2
1 1 1 1 1 1 1 1 1 1
10    
2 2 2 2 2 2 2 2 2 2

Then write 0 0 as

1 1 1 1 1 1 1 1
00 a  b 
2 2 2 2 2 2 2 2

To evaluate these constants a and b, use orthogonal and orthonomal properties

a b
  0 ; a 2  b 2  1 ; a  b
2 2
1 1
a 2  a 2  1  2a 2  1  a  ;b
2 2

1 1 1 1 1 1 1 1 1 1
So 0 0    
2 2 2 2 2 2 2 2 2 2
 1 1 1 1
Again, the wavefuntion 1  1   
2 2 2 2

1 1
If we consider j1  s1  ; j2  s2  the spin orbitals then
2 2

The three symmetric wavfunctions  S are

j1,m1 j2,m2
J ,m
1 1 1 1
11    (1) (2)
2 2 2 2

1 1 1 1 1 1 1 1 1 1 1
10       (1) (2)   (2) (1)
2 2 2 2 2 2 2 2 2 2 2

1 1 1 1
1 1      (1)  (2)
2 2 2 2

And the antisymmetric wavefunction  A is

1 1 1 1 1 1 1 1 1 1 1
00       (1) (2)   (2) (1)
2 2 2 2 2 2 2 2 2 2 2

To construct the total wavefunction of the atom,

1. we need to construct the coupled wavefunction for the spin orbital S M S

2. we need to construct the coupled wavefuntion for the space orbital L M L

3. Construct an antisymmetric wavefunction from the result of 1 and 2

Example (1) : For 1s 2 we have terms 1S

1  0 ; ml1  0 2  0 ; ml1  0
L  0, M L  0

L M L  00  1s(1)1s(2)

This is the only possibility because the wavefunction will be same even we interchange
the electrons.
This is symmetric, so we have to multiply with the antisymmetric wavefunction of spin
orbital to get the wavefunction of the term 1S

1
S 00  L M L S M s  L M L
1
S
S Ms A
 1s (1)1s (2)  (1)  (2)   (2)  (1) 
2
1 1s(1) (1) 1s(1)  (1)
  1s  1s   0 0
2 1s(2) (2) 1s(2)  (2)

Example (2) : For 1s 2s , we have terms 1S and 3S

1  0 ; ml1  0 2  0 ; ml1  0
L  0, M L  0

L M L  00  1s(1)2s(2)

Now it is possible to make symmetric and antisymmetric wavefunctions by interchanging

the electrons.

1 1
L ML S
 1s(1)2s(2)  1s(2)2s(1) and L M L A
 1s(1)2s(2) 1s(2)2s(1)
2 2

S 00  L M L S M s  L M L
1
S
S Ms A

1 1
 1s(1)2s(2)  1s(2)2s(1)  (1)  (2)   (2)  (1) 
2 2
1  1s(1) (1) 2 s(1)  (1)  1  1s(1)  (1) 2 s(1) (1) 
    
2  1s(2) (2) 2 s(2)  (2)  2  1s(2)  (2) 2 s(2) (2) 
1    1   
  1s 2s  1s  2s     0 0  0 0 

2 2

Similarly we get

3
S 01  L M L S M s  L M L A
S Ms S

1
 1s(1)2s(2)  1s(2)2s(1) (1) (2)
2
1 1s(1) (1) 2s(1) (1)
  1s  2s   0 0
2 1 s (2) (2) 2 s (2) (2)
 3
S 00  L M L S M s  L M L A
S Ms S

1 1
 1s(1)2s(2)  1s(2)2s(1)  (1)  (2)   (2)  (1) 
2 2
1  1s(1) (1) 2 s(1)  (1)  1  1s(1)  (1) 2 s(1) (1) 
    
2  1s(2) (2) 2 s(2)  (2)  2  1s(2)  (2) 2 s(2) (2) 
1    1   
  1s 2s  1s  2 s     0 0  0 0 

2 2

And

3
S 0 1  L M L S M s  L M L A
S Ms S

1
 1s(1)2s(2)  1s(2)2s(1)  (1)  (2)
2
1 1s(1)  (1) 2 s(1)  (1)
  1s  2s   0 0
2 1s(2)  (2) 2 s(2)  (2)

Property of C.G. Coefficient

J1  J 2  J
j1 j2 m1 m2 | j1 j2 J m   1 J 2 J1 m2 m1 | J 2 J1 J m

J1 J 2 m1 m2 | J1 J 2 J m    m, m1  m2 
 J1  J 2  J !  J  J1  J 2 !  J  J 2  J1 !  2 J  1
 J  J1  J 2  1!
 1k  J1  m1 !  J1  m1 !  J 2  m2 !  J 2  m2 !  J  m !  J  m !

k
k !  J1  J 2  J  k !  J1  m1  k !  J 2  m2  k !  J  J 2  m1  k !  J  J1  m2  k !
For two electrons

1 ; 2

1 1 2 1 L M L
1
L ML
S
  1 1 L M L   2 1 L M L 
2
A 1 2 1 2

1  1 2 L 
 1 1 L M L   1 1 1  2  L M L
2 
1 2 2

1  1 2 L  1
1
L ML MS  1  2 L M L   1 1 1  2 L M L
2 
1 2 2
 1  1 2 L  3
3
L ML MS  1 1 L M L   1 1 1  2 L M L
2 
1 2 2

For equivalent electrons we have l1  l2 . The singlet function (S = 0) will vanish unless L
is even. The triplet function (S = 1) will vanish unless L is odd. Thus the wavefunction
for the equivalent electrons will vanish unless L + S = even.

THREE ANGULAR MOMENTA

Here we will evaluate the coupled wavefunction arising from coupling of three angular
momenta. The points to be noted here that,

When three angular momentum operators are J1 , J2, J3 are coupled to form J, the
possible values of J are independent of the coupling scheme.

However, the eigenfunctions are dependent of the detailed of the coupling scheme.

In the following we will see it.

J  J1  J 2  J3

1 1
Let us take j1  1 ; j2  ; j3 
2 2

Case 1: Scheme-1

j12  j1  j2
j  j12  j3

 3 3 3 1
 , 
1 3  2 2 2 2
j1 j2  j12  1    wavefunctions
2 2  3 1 3 1
, 
 2 2 2 2
 1 1
 
1 1  2 2
j1 j2  j12  1    wavefunctions
2 2  1 1

 2 2

1 3 3 1 1
j1 j2 j12 m12  1  11 …..Eqn. (1)
2 2 2 2 2
Applying J  on both sides

1 3 3 1  3  3  3  3  1 3 1
J 1    1    1 1
2 2 2 2  2  2  2  2   2 2 2
1 1 3 1 3 1 3 1
 3 1  1
2 2 2 2 2 2 2 2

1 1 1 1 1 1
J 1 1  J1 1 1  J 2 1 1
2 2 2 2 2 2
1 1 1 1  1  1  1  1  1 1
 11  1  11  1  1 0     1    1  1 1 
2 2 2 2  2  2  2  2  2 2
1 1 1 1 1
 10  11
2 2 2 2 2

So,

1 3 1 2 1 1 1 1 1
1  10  11  ….. Eqn. (2)
2 2 2 3 2 2 3 2 2

Similarly,

1 3 3 1 1
1   1 1  ….. Eqn. (3)
2 2 2 2 2

Applying J  on both sides

1 3 3 1  3  3   3  3   1 3 1
J 1       1       1  1 
2 2 2 2  2  2   2  2   2 2 2
1 15 3  1 3 1 3 1 3 1
    1   1 
2  4 4 2 2 2 2 2 2 2
 1 1 1 1 1 1
J 1 1   J1 1  1   J 2 1  1 
2 2 2 2 2 2
1 1 1
 11  1   1 1  1  1 0 
2 2 2
1  1  1   1  1   1 1
    1       1  1  1
2  2  2   2  2   2 2
1 1 1 1 1
 10   1 1
2 2 2 2 2

So,

1 3 1 2 1 1 1 1 1
1   10   1 1 ….. Eqn. (4)
2 2 2 3 2 2 3 2 2

Now we can write

1 1 1 1 1 1 1
1 a 10 b 11 
2 2 2 2 2 2 2

Using orthonormal & orthogonal properties:

a 2  b2  1
b2 a 2 b
  b2  1  0
2 3 3
1 2 1
3 b2  a 2  b a  
 1 2 3 3
2 b
a
2 2
b
3

So,

1 1 1 1 1 1 2 1 1
1  10  11  ….. Eqn. (5)
2 2 2 3 2 2 3 2 2

Now we can write

1 1 1 1 1 1 1
1   a1 1 0   b1 1  1
2 2 2 2 2 2 2
 a1 2 b1 a12  b12  1
 0
3 3
b
 a1   1 2 1
2 b1   a1 
3 3

1 1 1 1 1 1 2 1 1
1   10   1 1 ….. Eqn. (6)
2 2 2 3 2 2 3 2 2

Next we will find

3
1 1
1   2
2
2 2
1 3 1
1   1
2 2 2
1 1 1
1   1
2 2 2
1 1 1
1   0
2 2 2

3 1
11 Calculate
2 2

3 1 3 3 1 1 1 1 1 1
22   11
2 2 2 2 2 2 2 2 2 2

3 1 1 3 1
J 22   2  2  1  2  2  1  21
2 2 2 2 2
3 1
 2 22
2 2
 3 3 1 1 3 3 1 1 3 3 1 1
J  J1  J 2
2 2 2 2 2 2 2 2 2 2 2 2
1  3  3  3  3  3 1 1 1
   1    1
2  2  2  2  2   2 2 2 2
1  1  1  1  1  3 3 1 1
   1    1 
2  2  2  2  2   2 2 2 2
3 3 1 1 1 1 3 3 1 1
  
2 2 2 2 2 2 2 2 2 2
3 1 3 3 1 1 1 1 3 3 1 1
 21   
2 2 2 2 2 2 2 2 2 2 2 2

3 1 3 1 1 1 3 3 1 1
11  a b 
2 2 2 2 2 2 2 2 2 2

a 2  b2  1
a 3 b b2
 0   b2  1
2 2 3
 a 3  b 4
 b2  1
b 3
a
3 3 3 1 1
b , a  
2 2 3 2

3 1 1 3 1 1 1 3 3 3 1 1
11   
2 2 2 2 2 2 2 2 2 2 2 2

Now will calculate the final wavefunction

1 3 1
j1 j2  j12  j3 ; J m  1   ; 11
2 2 2
1 31 11 3 33 1 1
  
2 22 12 22 2 22 12 2 2

j1 j2  j12  j3 ; J m 
1 3 1 1 2 1 1 1 1 1  1 1 3 1 1  1 1
1   ; 11   10  11     11 
2 2 2 2 3 2 2 3 2 2  2 2 2  2 2  2 2
2 1 1 1 1 1 1 1 1 1 3 1 1 1 1
 10  11   11 
2 3 2 2 2 2 2 3 2 2 2 2 2 2 2 2 2
 2 1 3 2  1  9 12
Check:     1
43 43 4 12 12

The other one

1 1 1 1 1 1 1
j1 j2  j12  j3 ; J m  1   ; 11 
2 2 2 2 2 12 2 2
1 1 1 1 1 2 1 1 1 1
 10  11 
3 2 2 2 2 3 2 2 2 2

1
1 1 
1 0
J 23  J 2  J 3 2 2 
Case 2:
J  J1  J 23  1
1 1
0 0
2 2

1 1 1 1 1 1
11  ….. Eqn. (1)
2 2 2 2 2 2

1 1 1 1 1 1 1 1 1 1 1 1
10     ….. Eqn. (2)
2 2 2 2 2 2 2 2 2 2 2 2

1 1 1 1 1 1
1 1    ….. Eqn. (3)
2 2 2 2 2 2

1 1 1 1 1 1 1 1 1 1 1 1
00     ….. Eqn. (4)
2 2 2 2 2 2 2 2 2 2 2 2

Now the coupled wavefunctions j1 j2 j3  j23  ; j m

1 1
1, 1 2
2 2
1 1
1 1 1,1
2 2 11 2 2  11 11
1 1
1 1 0
2 2
1 1
1  0 1,1
2 2
 1
J 1 1 2 2   2  2  1  2  2  1  1 1 2 1
2
1
  4 1 1 2 1  2 1 1 2 1
2

J  1 1 1 1  J1 1 1 1 1  J 2 1 1 1 1
1 1
 11  1  11  1  1 0 1 1  11  1  11  1  1 1 1 0
2 2
 1 0 11  11 1 0

1 1
11 2 1  11 1 0  11 1 0 ; 1 1 1 1  a 1 0 1 1 23  b 1 1 1 0 23
2 2

a b a 2  b2  1
 0
2 2  2b 2  1  b  
1
 a  b 2
1
a
2
1 1
1111  1 0 1 1 23  11 1 0 23
2 2
1  1 1 1 1 1 1 1 1 1 1  1 1 1 1 1
      11  10
2 2 2 2 2 2 2 2 2 2 2  2 2 2 2 2

1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1
1 1 1 1  1 1   11   10
2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2

1 0 11  11 0 0 23
1 1 1 1 1 1 1 1 1 
 11    
22 2 2 2 2 2 2 2 
1 1 1 1 1 1 1 1 1 1
 11   11 
2 2 2 2 2 2 2 2 2 2

So all the wavefunctions J  1 m  1 are not same, it depends on the coupling scheme. In
this lecture we came to know the procedure of evaluating the coupled wave
functions.Then we made the total wavefunction antisymmetric by multiplying symmetric
L M L with antisymmetric S M S and vice versa. Then we prove that for three
angular coupling, the final wavefunctions depend on the detailed coupling scheme. It
should be noted that, under a coupling scheme, the wavefunctions are orthogonal. But the
wavefunctions should not be orthogonal for different coupling scheme.