Final Atomic and Molecular Physics - Notes

BANSAL ACADEMY CHANDIGARH
SCF-19, Sector 16-D, Chandigarh
Atomic and Molecular Physics

Notes
SPECTROSCOPY
* What is spectroscopy?
Spectroscopy is that branch of science in which we deal up with the observation and interpretation of radiation emitted and
absorbed by atoms and molecules and also it through light on their structure
 It provides information not only about arrangement and motion of outer electrons but also about internal electrons (X-rays
spectroscopy)
 and it also provides information about angular momentum, magnetic dipole moment distribution of charge and magnetism
of the nucleus (NHR spectroscopy).
* How we know about Sun?

Light from Sun and its spectra. We can match radiation spectra of any planet with radiation spectra of any element and
confirm its presence on that planet.
# Types of spectra: (1) Emission spectra (ii) Absorption spectra
# Emission spectra:
Here we have gas in its atomic form and to get radiation from it we have to excite the atoms of gas.
# Ways to excite the sample to radiate:
Temperature * Electroluminescence
Radiation * Chemiluminescence
* Photoluminescence
* Fluorescence and Phosphorescence
* Electroluminescence:
Excitation by accelerating the electric charge particles through the sample.

* Chemiluminescence: Excitation is done by energy released in chemical reaction.
* Photoluminiscence: Here sample excites by absorbing the photons (light)
(a) Fluorescence:
In fluorescence after removal of incident light effect vanishes immediately.
1
(b) But in phosphoresce effect exists even after removal of incident light for a short span of time
We can make a graph on wave no scale of radiation spectra (emission spectra) we get on black screen.
Length of spectral line indicates about intensity of radiation of that wave no. where intensity means no of photons of particular
brightness.
Why we get bright lines: Since photons are striking the screen so they will produce brightness.
* Since we want to know about all the possible photons that our sample can emit hence we heat up the sample at high
temperature.
In emission spectra electron excites to excited state by absorbing the energy and when it comes to lower level of energy it
emits a photon.
Que. Why wave number scale? Why it is not of frequency or wavelength scale? When a light passes through various
media then what remains constant for it?
(1) Wave length (2) frequency (3) wave number
Ans: Frequency and wave no both remains constant but wave length changes. Since frequency and wave number both remains
constant when light passes through various media so we can choose anyone of them for scaling purpose. But why wave
number is preferred over frequency?
c
Since frequency 
vacume
1
Wave number 
vac
Hence frequency is generally a large number and that’s why we prefer wave number for scaling smoothness.
# Units of wave number:   m 1 or cm 1

1cm 1  1.239 104 eV
1eV  8066cm 1
# Obsorption spectra
2
In obsorption spectra we want to know that what kind of photons can be obsorbed by the atom
# Why bright background?

Since light is incident on the sample due to this light background is bright.
# Why you are obtaining dark lines?

Since atoms in sample will obsorb some particular photons and these photons will be missing in the light that is going to the
screen and that’s why there are dark lines.
# Why they are faded dark lines?

8
Since the obsorbed photon will transit electron one of excited state and after approximately 10 s it will return to G.S and
may emit same photon and it is emitted in random directions and still there is a probability that it may be emitted in the same
direction as of incident photon and in that case it will strike the same position on wave number scale (screen).
# If we will superimpose the emission and absorption spectra of the same sample then lines will coincide perfectly.
But some lines will be missing in obsorption spectra.
Example: In emission spectra of H-atom we obtain Lyman, Balmer, Paschen, Bracket, Pfund all series but in obsorption
spectra we just get Lyman series. This happens because while observing obsorption spectra on sample is in chilled
environment and hence mostly atoms are in the ground state that’s why we only obtain Lyman series.
# At what temperature you will obtain Balmer series in case of obsorption spectra?
Obviously to obtain Balmer series along with Lyman series there should be appreciable population of atoms in n = 2 level.
We need temperature T  105 k to get Balmer series.
# Experimently observed H-spectra (emission spectra)
3
F  E f  Ei
E  h
hc
  hc
vac
# Bohr postulates: Bohar model was given to explain the experimently observed spectra for hydrogen atom.
Hydrogen like atoms: One electron system
He , Li  , Be3 ..............
Note: Li, Na, K, Rb also effectively one electron system but bohars theory not valid to them.
Bohr postulate: Electron revolves in circular orbits around the nucleous due to coulomb attraction of the nucleous.
People to bohr: Since infinite number of circular orbits possible around the nucleous then in which particular orbits electron
is orbiting.
Bohr replied via second postulate: Electron can revolve in those circular orbits only in which the magnitude of the angular
momentum of the electron is L  n
This postulate represents quantization of angular momentum for the electron and this quantization of angular momentum leads
to the quantization of energy levels.
# People to Bohr: Since direction of velocity of electron is changing from point to point on the circular path, so it’s a
accelerating charged particle and from electromagnetic theory an accelerating charged particle should emit radiation so after a

little time later the e should fall within the nucleous via a spiral path. But obviously its not happening there because universe
exist then what happening there actually?

Bohr third postulate: Bohr replied via a postulate and according to him the energy of e in a particular circular orbit is fixed,
constant or electron is revolving in stationary orbits or electrons is not emitting radiations while revolving in a particular orbit.
Bohr fourth postulate: Radiation is emitted in an atom when an electron make transition from a higher level to lower energy
level the frequency of this radiation is given as
h  E2  E1
4
E2  E1

h
Bohr model (with infinite nuclear mass consideration)

mP  1836me
Mathematical version of Bohr postulate:
F12  F electron  F coulombic

1  ze  e 
force on 1 due to 2  rˆ
4 0 r2
m 2
To sustain circular motion there will be a centrifugal force pointing away from the centre and its magnitude is
r
For mechanical stability of electron both forces will balance to each other
F  F centrifugal
1 2e 2 m 2
 (1)
4 0 r 2 r
# Mathematical version of Bohar postulates: L  n
n  1, 2, 3..................
where L  m r
So mr  n (2)
# Radius: We have equation (1) and (2)

1 ze 2 m 2
 1
4 0 r 2 r
m r  n  2
n
For equation (2) 
mr
5
Put this in (1)

1 ze 2 mn 2 2

4 0 r 2 rm 2 r 2
4 0 n 2 2
r (3)
mze 2
n2
r  0.59  A A  1010 m
z
1
r
m
n
Velocity: 
mr
In this equation of velocity we can put value of r from equation (3)
n  mze 2

m  4 0 2 n 2 
ze 2

4 0 n
  2.18 106 m / s
Here  is independent of mass
# Total energy: E  K  E  P  E
1 2 1 ze 2
E m 
2 4 0 r
We can put values of velocity and radius
1 mz 2 e 2 z 2 me 4
E 
2  4 0 2 n 2 2
 4 0 
2
n2 2
1 mz 2 e 4
E
2  4 0 2 n 2 2
z2
En  13.6  eV.
n2
.  1.6 1019 J
1eV
Here Em
Energy directly proportional to mass
# Time period (T)
2 r
T

2 r  total distance around nucleous
  velocity
4 0 n 2 2
4 0 n 2
T  2  
mze2 ze2
2  4 0   n 
2 3
T
m  ze2 
2
6
1 n3
T , T 2
m z
1
# Frequency f 
T
m  ze2 
2
f 
2  4 0   n 
2 3
f m
z2
f 
n3
2
# Angular frequency: T

2

T
2  m  ze2 
2

2  4 0   n 
2 3
m  ze2 
2

 4 0   n 
2 3
m
z3

n3
# Explanation of experimentally obtained-spectra: This will be done by postulates. According to IV postulate the frequency
of photon emitted is given as
E2  E1

h
1 1 Mz 2e4 1 Mz 2e4 
    
h  2  4 0 2 n22 2 2  4 0 2 n12 2

1 Mz 2e4  1 1 
   
2h  4 0 2 2  n12 n22 
h
By putting 
2
1 Mz 2e4 4 2  1 1 
    
2 16 2 02 h 2  n12 n22 
7
Mz 2e 4  1 1 
   
8 02 h3  n12 n22 
c
Since   c
vac
  c
Mz 2e 4  1 1 
So  c    
8 02 h3  n12 n22 
1 Mz 2e4  1 1 
    
vac 8 02 h3c  n12 n22 
Me 4
Now put  R
8 02 h3c
where R is Rydberg constant for infinitely heavy nucleous. R is same for all atoms
R  m
R  109737cm 1
# The selection rule for transitions were given by bohr as
n  can be anything
# Bohr model with finite nuclear mass consideration: There was a little error in position of transitions lines on wave
number scale. So to explain that bohr removed his assumptions of infinitely heavy nuclear mass.
Now if we consider the finite mass of the nucleus, then it will be two body problem and both revolving about there centre of
m1m2
mass this two body problem by using reduced mass concept and according to that a single particle of mass  .
m1  m2
1
# Radius: Since r 1
m
For finite mass nucleus
1
r'  2

Dividing equation (2) by (1)
r' m

r 
m
r'  r

m n2
So rn'   0.53  A
 z
This concept can be applied to any two body problem.
# Velocity: v '  v
Because velocity was independent of mass
# Energy: Em
E' 
E' 

E m
8

E' E
me
 z2
E'  13.6 ev
me n2
# Time period
1
T 1
m
1
T '  2

Dividing equation (2) by (1)
T' m

T 
m
T '  T

# Frequency: f m 1
f '  2
From equation (1) and (2)
f' 

f m

f ' f
m
# Angular frequency: w  2 f
m 1
'   2
' 

 m

 '  
m
1 1
we know v  R z 2  2  2 
 n1 n2 
Me 4
R 
8 02 h3c
Here R  m
So Ratom  
But m
So spectra will shift towards left on wave number scale but on wavelength scale will shift towards right.
But why   m ?
mM
Because 
M m
9
m

m
1
M

This term will be positive and if this term is positive then clearly   m.
# Rydberg constant in finite nuclear mass consideration: Since
R  m (1)
Ratom    2
Dividing equation (2) by equation (1)
Ratom 

R m

So Ratom   R
m
Here R  109737cm 1
Question: What is RH  ?

RH   R
m
1836 me
RH   R
1837 me
1836
where  me
1837
So RH  109677cm1
RD  ?
Rydberg constant for deuterium
2
1 H  deuterium
Here m p  mn
So mass of nucleus  2 m p

RD   109737cm 1
me
me  2 1836me

2 1836me  me
3672
 me
3673
3672
So RD  109737cm 1
3673
RD  109707cm 1
10
# Rydberg constant for tritium: RT  ?

3
1 H tritium has 2 neutron 1 proton so mass of nucleus 3m p
So RT  109717cm 1
RH  109677cm1
RD  109707cm 1
RT  109717cm 1
RHe  109722cm 1
Graphical variation of Rydberg constant with mass number A:
Discovery of Heavy Hydrogen Deuterium

There was a faded lines near to each spectral line obtained for H-atom in experimentally observed spectra and later it was
confirmed that this line is due to presence of deuterium atom in the sample.
Position of H  line for Deuterium:
1 1
  RD z 2  2
 2
 n1 n2 
1 1
  109707  1     cm 1
2
4 9
5
 109707  cm 1
36
  15237.08cm1
This is H  line.
For H-atom H  line
 5  1
 H  109677  1  cm
 36 
 15232.92cm 1
11

# Positronium atom: Replace proton by e positron in hydrogen atom it will become positronium atom.

Positron  e

(anti particle of e )
charge  e
mass  me
This is two body problem so we can use reduce mass concept
me  me

2me
me

2
1
# Radius: r 1
m
1
r'  2

m
r' r

me n2
r'  2  0.53  A
me z
n2
r '  2  0.53  A
z
# Velocity: Velocity will remain same because velocity not depend on mass
z
v  2.13  106  m / sec
n
# Energy: We know
Em 1
E'   2
12

E' E
m
1 z2 
E '   13.6  2  eV
2 n 
# Muonium atom:
Trick 1: Where “ium” in background then replace nuclear particle. But if there is “ic” in background of the name then replace
electron.
Now in this case we can not replace P by muon  because of charge difference of proton and muon but we can replace
proton by antiparticle of muon (anti muon)
charge  e
mass  m  207 me
This is two body problem we can reduce it to one body problem by reduced mass concept:
m
(1) Radius: r' r

208 n2
r'  0.53  A
207 z
# Velocity will remain same

E' E
me
207  z2 
  1  13.6  2  eV
208  n 
# Muonic atom: In muonic atom we will replace muon by electron
Two body problem reduced to one body problem by using reduced mass concept
836  207me2

1836  207  me
  186.02me
me
# Radius: r' r

1 n2
r'  0.53  A
186.02 z
# Binding energy of electron in n th level:
13
Binding energy in n th level: Energy required to remove electron from n th level and to send it to n   level (to make it
free)
E  ve because energy required
B.E   Enth
B.E  E  Enth E  0
B.E   Enth

# Ionization energy: Ionization energy is the energy required to remove its outermost valence e from an isolated atom.
For example: Na 1s 2 2s 2 2 p 6 3s1
1
Energy to remove 3s electron is I.E of Na atom
I.E = 13.6 eV
Ionization energy = 13.6 eV
Ionization energy  13.6V
Term symbol
Term spectroscopic

For single e system For multi-electron system
 
For equivalent e for non-equivalents e

(1) For single e system: n2s1LJ  term symbol

For e in 1S:
Multiplicity  2S 1
L 0 s
L 1 p

 

 L  2  d 
L  3  f 
 

and so on 
n  1,  0
14
 L0
1
S
2
1
 S
2
J  L  S to L  S
1 1
J  0 to 0 
2 2
1 1
 J , 2S  1  2   1  2
2 2
Term symbol  1 S1/ 2
2

For e in 2p:
1
 1, S 
2
J  L  S to L  S
1 1
J  1 to 1 
2 2
1 3
J to
2 2
1 3
or J ,
2 2
So term symbol  2
P1/2  , 2 P3/2
(2) For atoms with multi-electrons:

(a) Non-equivalent electrons having different values of n and :
Example: 3p 4d
 1, 2 1 1
1 2
S1  , S 2 
2 2
L 1  2 to 1  2 S  S1  S2 to S1  S2
L  1  2 to 1  2 1 1 1 1
S  to 
2 2 2 2
L  1 to 3 S  0 to 1
 L  1, 2, 3 S  0, 1
L  1, S  0 L  1, S  1
J  L  S to L  S J  1  1 to 1  1
J 1 J  0 to 2
For L  1  p J  0, 1, 2
2 s 1
p1  1 p1 L 1 p
2 s 1 2 s 1 2 s 1
p0 , p1 , p2
3 3 3
p0 , p1 , p2
15
L  2, S  0 L  2, S  1
J  2  0 to 2  0 J  2  1 to 2  1
J 2 J  1 to 3
L2D J  1, 2, 3
2 s 1
D2  1D1 term symbol L2D
3
D1 , 3 D2 , 3 D3
L  2, S  3 L  3, S  1
J  3  0 to 3  0 J  3  1 to 3  1
J 3 J  2 to 4
L 3 F J  2, 3, 4
1
F3 L 3 F
3
F2 , 3 F3 , 3 F4
So term symbols are  1 p1 , 3 p0 , 3 p1, 3 p2 , 1D2 , 3D1, 3D2 , 3D3 , 1F3 , 3F2 , 3F3 , 3F4
(b) For equivalent electrons:
2 p2  2 p 2 p 1
S1  , S 2 
1
2 2
1  1, 2 1 S  S1  S2 to S1  S2
L  1  1 to 1  1 1 1 1 1
S  to 
2 2 2 2
L  0 to 2 S  0 to 1
L  0, 1, 2 S  0, 1
Here only those combinations are allowed when L = even, S = even or L = odd, S = odd. So
(1) L  0, S  0
J 0
For L 0S
1
S0
(2) L  2, S  0
J 2
For L  2d
1
D2
(3) L  1, S  1
J  1  1 to 1  1
J  0 to 2
J  0, 1, 2
For L 1 p
2S 1  2 1  3
3
So p0 , 3 p1 , 3 p2
So term symbols  1S0 , 1D2 , 3 p0 , 3 p1 , 3 p2 .
For more than two electron system:
16
L  ML
L   MS
Important points:
(1) Highest S value  lowest energy
(2) Highest L value  lowest energy
(3) Low j value  lowest energy
For half filled orbit and for less than half filled orbit
(4) Higher j value  will have lower energy for more than half filled orbit.
Example 1: How much does the total angular momentum quantum number J change in the transition of Cr 3d 6   atoms as it

ionize to Cr 3 3d 4 ? 
(a) increase by 2 (b) decrease by 2 (c) decrease by 4 (d) does not change

Solution: In Cr 3d 6 state 
L  ML
L   2  2   11  0  1  2
L  4 1 1  2
L2
1 1 1 1 1 1
L  MS      
2 2 2 2 2 2
1
L   MS  4  2
2
 S 2
So J  L  S to L  S
J  2  2 to 2  2
J  0 to 4
or J  0, 1, 2, 3, 4
This orbit is more than half filled so lower J value  higher energy and vice versa
So J = 4  lower energy
Now for Cr
3
3d  4
L  ML
L   2 1  11  0  1
L  2  11
17
L2
Similarly S  MS
1 1 1 1
S   
2 2 2 2
1
or S  4  2
2
S 2
or J  L  S to L  S
J  2  2 to 2  2
J  0 to 4
J  0, 1, 2, 3, 4
This is the case of less than half filled so lower J value  lower energy. So
J = 0  lowest energy
So J decreases from J = 4 to J = 0
Difference = 4
So option (c) is correct.
Example 2: The ground state electronic configuration of

22
Ti is  Ar  3d 2 4S 2 , which state, in the standard spectroscopic
notations, is not possible in this configuration?
1 1 1 3
(a) F3 (b) S 0 (c) D2 (d) P2
Correct answer: (a)
12 13
Example 3: The LS configuration of the ground state Mg , Al , 17Cl and 18
Ar are respectively
3
(a) S1 , 2 P1/2 , 2 P1/2 and 1S0 (b)
3
S1 , 2 P3/2 , 2 P3/2 and 3S1
1 2 2 3 1
(c) S 0 , P1/2 , P3/2 and S 0 (d) S0 , 2 P3/2 , 2 P1/2 and 3S1
Correct answer: (c)
12
Solution: (1) Mg :1s 2 , 2s 2 , 2 p 6 , 3s 2
L   M L  2  0  0
1 1
S   MS   0
2 2
J  L  S to L  S
J 0
It can be solved by another method: 3S 2  3S 3S

Electrons in same orbit 1  0, 2 0
L0
1 1
S1  , S 2 
2 2
1 1 1 1
S1   to 
2 2 2 2
18
S  0, 1
L  0, S  0  even value of L with even value of S only those combination are allowed
Term symbol: S 0  for

1 12
Mg
(2) For
13
Al  1S 2 , 2S 2 , 2 p 6 , 3S 2 , 3 p1
1
For 3 p1  S 
2
1
J   S to  S
1 1
J  1 to 1 
2 2
1 3
J to
2 2
1
and 2S  1  2   1  1  1  2
2
2
So p1/2 , 2 p3/2
Here orbit is less than half filled, so lower j value have lower energy. So
2
p1/2  for ground state
(3) For
17
Cl  1S 2 , 2S 2 , 2 p 6 , 3S 2 , 3 p 5
For 3p5
L   M L  2 1  0  2   11
L   M L  2 1
L 1
1 1 1 1 1
S   MS         
2 2 2 2 2
1
S
2
J   S to  S
1 1
J  1 to 1 
2 2
1 3
J ,
2 2
2
p1/2 , 2 p3/2
Here orbit is more than half filled, so higher j value will have lower energy.
2
p3/2  for ground state
(4) For
18
Ar  1S 2 , 2S 2 , 2 p 6 , 3S 2 , 3 p 6
For 3p 6
19
L   M L  2 1  0  2   2  1
L  ML  0  0  2  0
L0
1 1 1 1 1 1
S   MS            
2 2 2 2 2 2
S 0
J 0
1
Term symbol: S 0
So option (c) is correct.
Example 4: Of the following term symbols of the np 2 atomic configuration 1S0 , 3P0 , 3P1 , 3P2 and 1D2 , which is the
ground state?
3 1 3 3
(a) P0 (b) S 0 (c) P2 (d) P1
Correct option: (a)
There are two types of coupling:

(1) L-S coupling: L 1  2  3 ............. n to 1  2  3 ............. n
or L 1  2 to 1  2
and S  S1  S2 to S1  S2
(1) J-J coupling: 1 , 2 , 3 ............., S1 , S2 , S3 .............

j1  1  S1 to 1  S1
j2  2  S2 to 2  S2
J  j2  j2 to j1  j2
Comparison between J-J coupling and L-S coupling:

For lighter elements: Spin-spin interaction and orbital-orbital interaction is stronger as compared to the spin-orbit interaction.
So L-S coupling is applied only for lighter elements.
For heavier elements: Spin-orbit interaction dominate over spin-spin and orbital-orbital interaction.
So J-J coupling is applied only for heavier elements.
So spin angular momentum and orbital angular momentum of individual electrons will combine to give total A.M(j)
Now in L-S coupling: J   S

(1) The angle between L and S is given by
J  J  1    1  S  S  1
cos  L, S  
2   1 S  S  1
(2) The angle between L and J :
20
J  LS
S  J L
S 2   J  L  J  L 
S 2  J 2  2 LJ  L2
S 2  J 2  L2  2SL cos  SL 
J 2  L2  S 2
cos  S , L  
2SL
J  j  j  1 2 , L2 
2
  1 2
, S 2  S  S  1 2
j  j  1    1  S  S  1
cos  S , L  
2   1 j  j  1
(3) Angle between S and J :
J  LS
L  J S
S  S  1  j  j  1    1

cos S  J  
2 S  S  1 j  j  1
Magnetic moment:
(1) Orbital magnetic moment:
 
2m
or   g   1  B
e
B 
 2m
Bohr magneton
(2) Spin magnetic moment:  S   g S S  S  1  B
Total magnetic moment:  j   g j j  j  1  B

J  J  1  S  S  1    1
gJ  1
2 J  j  1
g J  lande’s g-factor
(1) For purely orbital motion:

S  0, j 
g j  g 1
(2) For purely spin motion:

 0, j  S
g j  gS  2
Quantum numbers:
(I) Principle quantum numbers (n):
21
(1) Its tells the energy of the electron.

(2) n tells about the orbit or shell
n = 1 (K-shell)
n = 2 (L-shell)
n = 3 (M-shell)
n = 4 (N-shell)

(3) It also tells about the distance between e and nuclear.
(II) Orbital quantum number  :

(1) Its tells about the shape of the orbital
(2) It tells about the orbital angular momentum
According to quantum mechanics, the magnitude of orbital angular momentum
   1
where is takes from 0 to n – 1
0   n 1
For n  1,  0 (s-subshell)
For n  2,  0, 1 (s-subshell)
  0  s  subshell 
 
  1  p  subshell 
For n  3,  0, 1, 2
  
s p d
(III) Magnetic orbital quantum number m  :
z m
z  cos 
cos   z
m
cos  
  1
m
or cos  
  1
where m from  to 
For 1
m  1 to 1
or m  1, 0, 1
So for m  1,  1
22
1
cos   
2
for m  1,  1
1
cos  
2
for m  0,  1
cos  0
(IV) Magnetic spin quantum number  mS  :

S z  mS
S z  S cos 
Sz mS
cos   
S S  S  1
mS
or cos  
S  S  1
1 1 1
For S , mS  , 
2 2 2
1 1
cos   ,
3 3
# Aufbar Principal:
for 1S 2S 2p 3S 3p 3S 4S 3d 4p 5S………………….
Pauli exclusion principle: No two electrons will have identical quantum or “The quantum states of different electrons will be
different”.
# Hund’s rule: According to this rule, electrons will prefer orbitals with parallel spins
23
# Larmour procession: “Electrons orbit process about the direction of magnetic field”. This effect is known as “Larmour
procession”
eB
Larmour frequency '  ' 
2m
Interaction energy:
In L-S coupling: E  a  S
or E  z 4  E hydrogen
Example 1: The value of the lande g-factor for a fine-structure level defined by the quantum number L = 1, J = 2 and S = 1 is
11 4 8 3
(a) (b) (c) (d)
6 3 3 2
J  J  1  S  S  1  L  L  1
Solution: g  1
2 J  J  1
2  2  1  11  1  11  1
g  1
2  2  2  1
622
g  1
4  3
1 3
g  1 
2 2
3
g
2
So option (d) is correct.
3
Example 2: The lande g-factor for the P1 level of an atom is
1 3 5 7
(a) (b) (c) (d)
2 2 2 2
Correct option: (b)
Example 3: The L, S, J quantum numbers corresponding to the ground state electronic configuration of boron z  51 are  
1 3 1 1
(a) L  1, S  ,J (b) L  1, S  ,J
2 2 2 2
3 1 3 3
(c) L  1, S  , J  (d) L  0, S  , J 
2 2 2 2
3
Example 4: If an atom is in the P3 state, the angle between its orbital and spin angular momentum vectors L and S is: 
1 1 1 2 1 1 1 3
(a) cos (b) cos (c) cos (d) cos
3 3 2 2
3
Solution: For P3 state
L = 2, J = 3, 2S + 1 = 3, S = 1
J  J  1  L  L  1  S  S  1
So cos   cos L  S   2 L  L  1 S  S  1
24
3  3  1  2  2  1  11  1
cos   cos L  S    2 2  2  1 11  1
 1 
   cos 1  L  S   cos 1  
 3
1
The term shift in cm
E z4
T    5.84 3 cm1
hc n   1
or T  z 4
Example 5: If the doublet splitting of the first excited state

2
P3/2  2 P1/2 of H atoms is 0.365cm 1 . Calculate the
corresponding separation for L
i
Solution: T  z 4
For L
i , z 3
 T L i
 34
For H, z 1
 T H  14
 T  L 34 
   81i
 T  H 14
 T L  81  T H  81 0.365  29.6cm1

i
Example 6:
(j – j) coupling:
For 2s1 , 3d 1
1
For 2 s1 , 1  0, s1 
2
J1  1  s1 to 1  s1
1 1
 J1  0  to 0 
2 2
1
or J1 
2
For 3d 1
1
For 3d 1 , 2  2, ss 
2
J2  2  s2 to 2  s2
25
1 1
 J2  2  to 2 
2 2
3 5
or J2  ,
2 2
J  J 2  J 2 to J1  J 2
1 3
For J1  , J2 
2 2
1 3 1 3
J   to 
2 2 2 2
J  1 to 2
J  1, 2
1 3
 J1 , J 2  J  , 
 2 2 1, 2
1 5
For J1  , J2 
2 2
1 5 1 5
J   to 
2 2 2 2
J  2 to 3
J  2, 3
1 5
 J1 , J 2  J  , 
 2 2  2, 3
Example 7: A hydrogen atom is in the orbital angular momentum state 1 , m  . If L lies on a cone which make a half
angle 30 with respect to the z-axis, the value of is _______________
Solution:
Lz  L cos 30
3
cos 30 
2
 3
 Lz    L
 2 
And Lz  m , L    1
3
So m    1
2
3
m    1
2
26
Given m 
3
So    1
2
3
 2
   1
2
By solving 3
2
Multiply by mr by equation (1)
n
m 2 rn2 vn2 1 ze2 mrn2


rn 4 0 rn2
n2 2 1
 ze 2 m
rn 4 0
n2 4 0
2
rn 
ze2 m
n 2 2 4 0
rn 
ze2 4
 n 2 0  h 2
rn   2   (2)
 me   z
0.53 A0
h2
rn   0.53 A0   (3)
z
For H-atom z=1
rn   0.53 A0  n 2
For n=1
r1   0.53 A0  90  bohr radius
Put the value of rn in equation (2)
nh znhe2
vn  
h 2  n 2 2h 0 n 2
2 m  2 0
me  z
 e2  z
vn    (4)
 2 0 h  n

2.18106 m /sec
vn   2.18  106 m / sec 

z
n
For H-atom, z = 1
vn 
 2.18 10 m / sec 
6
n
For n=1
2.18 106 m / sec137
v1 
137
27
3 108 m / sec c
v1  
137 137
v1 1
    fine structure constant
c 137
vn
Angular velocity: n 
rn
2
Time period: Tn 
n
2 rn
Tn 
vn
1
Frequency: f n 
Tn
vn
fn 
2 rn

Energy of e in the nth orbit: En  K .E  P.E
1 2 1 ze2
En  mvn 
2 4 n r
2
1  e2 z  ze2
En  m   
2  2 0 hn   h2 0 n 2 
4 0  
 me  z 
2
1me 4 z 2 z 2e4 m
En  
8 02 h 2 n 2 4h 2 02 n 2
me4 z 2  me 4  z 2 
En      2 2  2 
8 02 h 2 n 2  8 0 h   n 
z2
En   13.6ev 
n2
me4
 13.6ev
8 02 h 2
Ionization energy or ionization potential: I .E  En
z2
I .E  13.6ev 
n2
For n = 1 to n = 2: We require E  E2  E1
E  3.4   13.6  ev
E  10.20ev
hc
Term value: E   hcv

28
En  13.6 z 2  1
Wave no. v   1
n
  
hc 

h 2  hc
 13.6   z 
2
   2 
 hc   h 

R
R  1.098 107 m 1 = Rydberg constant

13.6
R  
hc
Hydrogen atom spectra:
(1) Lymann series: Lies in UV region
1 1 1
 R  2  2 
L  n f ni 
n f  1  for lymann series
ni  2, 3, 4............
For ni  2, n f  1  L line  maximum wavelength
For ni  3, n f  1  L line
For ni  4, n f  1  L line
For ni   n f  1  L line  lowest wavelength
(2) Balmer series: Lies in visible region

1 1 1
 R  2  2 
H  n f ni 
n f  2  for Barmer series
ni  3, 4, 5............
For ni  3, n f  2  H line  maximum wavelength
For ni  4, n f  2  H  line
For ni  5, n f  2  H line
For ni   n f  2  H line  lowest wavelength
(3) Paschen series: Lies in IR region
1 1
 p  R  2
 2
 3 ni 
n f  3, ni  4, 5............
For ni  4, n f  3  p
For ni  5, n f  3  p
For ni  6, n f  3  p
(4) Bracket series: Lies in IR region
29
1 1 1
 R  2  2 
B  4 ni 
nf  4
ni  5, 6............
For ni  5, n f  4  B
For ni  6, n f  5  B
For ni  7, n f  4  B
(5) Pfund series: Lies in IR region

1 1 1 
 R  2  2 
p f  ni 
nf  5
ni  6, 7............
For ni  6, n f  5  p f
For ni  7, n f  5  p f 
For ni  8, n f  5  p f
hc
shortest 
 E largest
mM
Reduced mass: 
mM
m  mass of e 
M  mass of nucleus = mass of proton
m

m
1
M
As M   [taking mass of nucleus large]
  m  as M  
All calculations which are taking by putting   m  as M  
Now taking reduced mass in all above calculation
 h2   n2
rn ,    2 0  as M  
 me   z
 h2   n2
rn , M   2 0 
 e   z
 
 h 2 0  n2
rn , M  
  mM  e 2  z
mM  
  
30
 mM   h 0 n 
2 2
rn , M    
 M   me  z 
2
mM 
rn , M    rn , 
 M 
Vn , M  Vn ,   velocity is same
  me 4  z 2
Energy of e in nth orbit: En ,     2  2
 8 0 h  n
2
  e4  z 2
En , M    2 2  2
 8 0 h  n
 mMe4  z2
En, M    2 
 2
  m  M  8 0 h  n
2
 M 
En , M    En , 
mM 
 M 
Rydberg constant: Rn , M    Rn , 
mM 
# Positronium atom:

A hydrogen like atom having one positron in the nucleus and one e around the nucleus
m positron  melectron 
mM

mM
m m
 e e
me  me
me2

2me
me

2
Radius  rpositronium  2   rn  H atom
Velocity  Vn  positronium  Vn  H atom
 En  H atom
Energy   En  positronium 
2
 Rn  H atom
Rydberg constant:  Rn  positronium 
2
Muonic atom: A hydrogen atom having one proton in the nucleus and one muon revolving around the nucleus is called
muonic atom one proton, one muon
31
m  207 me
mp  1836me
mM

mM

 207me 1836me 
 207me   1836me 
  186me
1
Radius  rn muonic   rn  H atom
186
Velocity of muon = Velocity of H-atom
Energy of muon   En muonic  186   En  H atom
Rydberg constant  Rmuonic  186  RH atom
Bohr modal  does not explain other spectrum except H-atom.
b k
Wilson-Sommerfield theory: 
a n
n  principle quantum number
k  azimuthal quantum number
b  minor axis
a  major axis
nr  n  k
n  1, 2..............
k  1, 2..............
k  0  then path of e  becomes straight line which is impossible
k  0 is not 0possible
(1) n  1, k  1
nr  0
b 1

a 1
b  a  equation of circle
(2) n  2, k  2
nr  0
nr  1, 2.................... equation of ellipse
The semi minor axis  a   n 2 a0

bohr radius
The major axis (a) is only determined by the principal quantum number.
Quantum number. (1) Principal quantum number (N)
 N tells the energy of e 
 N tells about orbit
32
N = 1 (K-shell)
N = 2 (L-shell)
N = 3 (M-shell)

Zeeman effect: When e interact with magnetic field
(1) Normal Zeeman effect: S = 0

E  g j M j B B
g j  1 for S  0 E  M j  B B
Selection rule: M J  0,  1
For example: P1  1D2

1
M J  0    lines
M J  1    lines
  lines are linearly polarized
  lines are circularly polarized
(1) When  
to magnetic field B  only  lines are observed
(2) When viewed  to magnetic field  both  lines and  lines are observed
Energy difference: E   B B
hc
E   hv

e
B 
2m
E  B B
v  
h h
33
B B e B
v  
h 2mh
hc
The wave number difference: E   v  hc

E
v 
hc
 B
v  B
hcc
e B
v   L ' = Lorentz’s number
2mhc
In terms of wavelength
1
v

1
v   
2
  v   2
e B 2
  
2mhc
No. of   lines

 2 J1  1
No. of   lines 2  J1  J 2 
For P1  D2
1 1
 
J11 J 2 2
Number of   lines  2 1  1
=2+1=3
Number of   lines = 2(1+2)
= 2(3) = 6
Total lines = 2J + 1
For
1
D2  J  2
Lines  2  2  1
=4+1=5
For P1  J  1
1
Lines  2 1  1
=2+1=3
(2) Anomolous Zeeman effect: S  0

Sodium  Z  11  1s 2 , 2s 2 , 2 p6 , 3s1 (ground state)
1s 2 , 2s 2 , 2 p 6 , 3s 0 , 3 p1 (excited state)
34
D1  2S1/2 to 2 P1/2
D2  2S1/2 to 2 P3/2
Cesium has same spectra as sodium.
For D1  line  2
P1/2  2 S1/2 
E  g J m j B B
J  J  1  S  S  1  L  L  1
gJ 
2 J  J  1
1 1
J ,  0, S 
2 2
gJ  2
1 1
J ,  1, S 
2 2
13
   11  1  1  1
22
gJ  1
13
2  
22
3
1  2  2
gJ  1 4
3
2
3 2 1 2
gJ  1   1 
4 3 2 3
2
gJ 
3
No. of lines in D1  4
35
For D2  line  2
S1/2  2 P3/2 
J  J  1  S  S  1    1
gJ  1
2 J  J  1
1 1
2
S1/2  S  ,J , 0
2 2
gJ  2
1 3
2
P3/2  S 
, J  , 1
2 2
35 13
      11  1
15 3
 2
22 22
gJ  1  1 4 4
35 15
2  
22 2
4
gJ 
3
E  g J m j B B
Degeneracy = 2J + 1
3
2
P3/ 2  J 
2
3
Degeneracy  2  1
2
=3+1
= 4 = (4 Mg value)
(3) Strong magnetic field (Paschen back effect): It strong magnetic field, L-S coupling breaks.
Interaction energy: E  E  ES

E  g m  B B  g S mS B B
g  1, g S  2
E   m  2mS  B B
Selection rules: M  2M S  1, 0
36
Levels splitted are depend upon energy

1
m  0, mS   E   B B
2
1
m  0, mS    E    B B
2
1
m  1, mS   E   m  2mS   B B  2  B B
2
1
m  0, mS   E   B B
2
1 1
m  1, mS   , E  0, m  1, mS  , E  0
2 2
1
m  0, mS   , E    B B
2
1
m  1, mS   , E  2  B B
2
Selection rule: M L  2M S  0, 1
M  2M S  1, 0

Hyperfine structure: Interaction of e , nucleus with magnetic field
F=I+J
I  angular momentum of nucleus

J  angular momentum of e
F  angular momentum of atom
F  I  J to I  J
37
F  0,  1
Selection rule: (Not allowed 0 to 0 transition)
0   0
3 3
J , I  (given)
2 2
3 3 3 3
F   to  , F  0, 1, 2, 3
2 2 2 2
For example:
F  0,  1
Lande’s interval rule: The energy difference between two hyperfine lines is proportional to highest value of F
E  F (highest value)
E  a  F  1  B B , F = lowest value
a = hyperfine structure constant
Rotational spectra: The molecules having non-zero permanent dipole moment will show spectra.
All hetero nuclear diatomic molecule shows rotational spectra
H , HBr
(1) For rigid body: [In microwave and IR region]
2
EJ  J  J  1
2I
m1m2

m1  m2
I = moment of inertia
I  r2
r  internuclear distance
1
In terms of wave number v 

38
hc
E  hcv J

2
E
vJ  J  J  J  1
hc 2 Ihc
h2 h
vJ  2 J  J  1  J  J  1
8 Ihc 8 2 Ic

B
v J  BJ  J  1 , B  rotational constant
v J  B  J  1

lowest value
h
B
8 2 Ic
Selection rule: J  1
Isotope effect: i  
I 
Ii  I
Bi  B
v  BJ  J  1  DJ 2  J  1
2
For non-rigid rotator:
EJ
v  , EJ  hcv, EJ  BJ  J  1 hc  DhcJ 2  J  1
2
hc
 EJ 
Intensity of spectra lines: I   2 J  1 exp   
 k BT 
As T  , I   2 J  1
Population:
 EJ  E0 
NJ g 
 1e k BT
N0 g2
E0  0
g1  2 J1  1
39
g2  2 J 2  1
E
NJ  J
In general   2 J  1 e kBT
N0
The value of J, for maximum population
N J
0
J
 EJ 
EJ EJ
  d
2e k BT
  2 J  1 e k BT
 0
dJ  k BT 

EJ
k BT

 2 J  1  k T
E J
d  2 
J  J  1   0
2e e 
B
k BT dJ  2I 
 2 J  1 2
2  2 J  1  0
k BT 2I
 2 J  1
2 2
2 0
2 Ik BT
 2 J  1
2 2
2
2 Ik BT
4 Ik BT
2
 2J 1
1 4 Ik BT 1
2
 J
2 2
Ik BT  4 2 1
2
 J
2
 8 2 Ic   k BT  1
J   
 h   2hc  2
k BT 1
J 
2 Bhc 2
k BT 1
J   maximum population at this value of J
2hcB 2
2
EJ  J  J  1
2I
v J  BJ  J  1
Separation between the lines = 2B
Vibrational spectra: Heternuclear show vibrational [observed is IR region]

(1) Harmonic oscillator: [for small amplitude]
40
 1
E   v   e
 2
v  0, 1, 3..........
hc
E hcv

 1
 v   e
E  2
v 
hc hc
 1
Wave number  v   v  e
 2
1 k
e 
2 
1
e 

(2) Anharmonic oscillator: [for large amplitude]
2
 1  1
Ev   v   e   v   e X e
 2  2
2
 1  1
Wave number  v   v   e   v   e X e
 2  2
X e  Anharmoncity constant
v   e 1  2 xe   2vX e

Lowest value
(1) Fundamental band [most intense]
 v  0 to v  1

Put lowest value
 v   e 1  2 X e 
(2) 1st overtone  v  1 to v  2  {less intense}
Selection rule v  1
Comparison:
41
The energy of rotational level is much less than the energy for a vibrational level. Therefore there are many rotational energy
levels in one vibrational energy level
v1 B i
 i 
v2 B 
Intensity I rayles  I stokes  I anti stokes  Erayl  Erayl
Raman spectra: If a beam of light passed through a substance, it is found with transmitted light small f4raction of light is
scattered having lines of low and high frequency
Lower frequency or energy  stokes lines
Higher frequency or energy  anti-stokes lines
Rotational Raman spectra: v J  BJ  J  1

J  J 2
v  v J  2  v J
v  B  J  2  J  3  BJ  J  1
v  B  4 J  6 
Selection rule: J  0,  2
v  B  4 J  6 
J  0, 1, 2, 3...........
42
Vibrational Raman spectra: v  1,  2.....

2
 1  1
v   v  e   v   e X e
 2  2
v   e 1  2 X e  2vX e 
X – Rays:
hc
(1) Continuous X – rays: E 

1 1 1
  z    R  2  2 
2
(2) Characteristics X – rays:
  ni n f 
  1 for K-series X-rays
  7.4 for L-series
  screening constant
1
Mosley’s law: v   z    ,   z  
2 2
X – rays are inverse photo-electric effect.
Laser emission involves three process:

(1) Emission: (i) Spontaneous emission (ii) Stimulated emission
(2) Absorption: Let us consider two energy levels E1 and E2 and these levels contains N1 and N 2 no. of atoms per unit
volume respectively. N1 and N 2 are number densities
43
If we incident a radiation of energy hv  E2  E1 , then absorption will take place i.e. atom will excited to energy Y level E2
(I) Rate of absorption: It is the number of atoms per unit volume per unit time absorbed
dN1
  N1 B12U V 
dt
B12  Einstein coefficient for absorption
U V   energy density per unit spectral frequency range
N1  number of atoms per unit volume in level 1
(II) Emission:
(1) Spontaneous emission: In this spontaneous emission process, atoms will spontaneously decay to lower rate
Rate of spontaneous emission. It is the number of atoms per unit volume per unit time emitted
dN 2
  N 2 A21
dt
A21  Einstein coefficient for spontaneous emission
N 2  number of atoms per unit volume in level 2
1
and A21 
 21
 21  life time of level 2 for transition in level 1
Now suppose a 3-level system. Then life time of level 2
1 1 1
 
2  21  20
Ax  A21  A20
This case is valid for more than 1 transition. Now
dN 2
  N 2 A21
dt
44
dN 2 N
 2
dt  21
dN 2 1
or  dt
N2  21

N2 t  1 

 21  0
Integrating ln N 2 N2  0 t
So N 2  t   N 2  0  et / 21
Number density of atoms will decay exponentially with time in spontaneous emission.
(2) Stimulated emission:
When a photon of frequency hv  E2  E1 in interacts with an excited atom, then incident photon is coherently
superimposed over emitted photon. Now these two photons induce the emission of more photons and go on multiplication.
Until certain power level is reached. This emitted light is known as laser light.
dN 2
Rate of stimulated emission:  N 2 B12U V 
dt
B12  Einstein coefficient of stimulate emission
dN 2 I
  N2
dt hv
I  intensity of beam
  beam cross-sectional area
v  frequency of beam
Two levels have same degeneracy than
B12  B21  B
Calculation of Einstein coefficients
 Ni BU V    N 2 A  N 2 BU V 
A 8 v3
 3  1.4 1015   E  ev  
3
or
B c
N2
 e  hv / kBT  e  2 1  B
 E E k T
N1
* Requirements of laser emission:

(1) Population inversion: Number of atoms in the upper state should be greater than lower state to achieve population
inversion.
(2) Minimum pumping must be required.
Laser rate equations: Suppose we have a 3-level laser. Here level 2 is a meta stable state whose life time is of the order of
103 sec or one multi-second.
Laser always take place from metal-stable state.
45
dN 3 N
Rate equation of level-3:  R 3
dt  32
dN 2 N 3 N 2 I I
Rate equation of level-2:    N2  N1
dt  32  31 hv hv
dN 2 N 3 N 2 I
    N 2  N1 
dt  32  21 hv
N 2  N1
N3  R 32 and N 2  R 31
dN 2 N
then  R 2
dt  21
46

Final Atomic and Molecular Physics - Notes

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BANSAL ACADEMY CHANDIGARH

SCF-19, Sector 16-D, Chandigarh

Atomic and Molecular Physics

* How we know about Sun?

# Ways to excite the sample to radiate:

Excitation by accelerating the electric charge particles through the sample.

In fluorescence after removal of incident light effect vanishes immediately.

# Units of wave number:   m 1 or cm 1

# Why bright background?

# Why you are obtaining dark lines?

# Why they are faded dark lines?

Bohr model (with infinite nuclear mass consideration)

Mathematical version of Bohr postulate:

F12  F electron  F coulombic

# Mathematical version of Bohar postulates: L  n

# Radius: We have equation (1) and (2)

Put this in (1)

# Rydberg constant for tritium: RT  ?

Graphical variation of Rydberg constant with mass number A:

Discovery of Heavy Hydrogen Deuterium

Position of H  line for Deuterium:

# Muonic atom: In muonic atom we will replace muon by electron

(2) For atoms with multi-electrons:

Example 2: The ground state electronic configuration of

It can be solved by another method: 3S 2  3S 3S

Term symbol: S 0  for

There are two types of coupling:

(1) J-J coupling: 1 , 2 , 3 ............., S1 , S2 , S3 .............

Comparison between J-J coupling and L-S coupling:

Now in L-S coupling: J   S

(2) The angle between L and J :

(3) Angle between S and J :

(2) Spin magnetic moment:  S   g S S  S  1  B

Total magnetic moment:  j   g j j  j  1  B

(1) For purely orbital motion:

(2) For purely spin motion:

(1) Its tells the energy of the electron.

(II) Orbital quantum number  :

(III) Magnetic orbital quantum number m  :

(IV) Magnetic spin quantum number  mS  :

Example 5: If the doublet splitting of the first excited state

m 2 rn2 vn2 1 ze2 mrn2

vn   2.18  106 m / sec 

Ionization energy or ionization potential: I .E  En

R  1.098 107 m 1 = Rydberg constant

(2) Balmer series: Lies in visible region

(5) Pfund series: Lies in IR region

(1) Normal Zeeman effect: S = 0

For example: P1  1D2

(2) Anomolous Zeeman effect: S  0

Interaction energy: E  E  ES

Selection rules: M  2M S  1, 0

Levels splitted are depend upon energy

Vibrational spectra: Heternuclear show vibrational [observed is IR region]

Rotational Raman spectra: v J  BJ  J  1

Vibrational Raman spectra: v  1,  2.....

X – rays are inverse photo-electric effect.

Laser emission involves three process:

(2) Stimulated emission:

* Requirements of laser emission:

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