Spark Institute of Physics

Max planck quantum theory

Packet of Energy – hv: According to Maxplank [Link]. Light is emitted in the form of
packets of energy. Each packets energy E = hv. h  6.6  1034 J .S
hc h.c 12400 1240
E   c  v  Joules E   6.25  1018 eV E   eV
   ( A0 )  (nm)

EM Spectra

Q. Find the Energy range of Visible light photons.

12400 12400
Emax    3.1eV
min 4000
12400 12400
Emin    1.8 eV (1.78 eV )
max 7000
Q. In a quantum of 20.8 1019 J how many photons of   5000 Ao are present.
12400 12400
E   2.48  1.6  1019  2.5  20.8  10 19 J
 5000
248
12400
 2.48  (1 photon Energy ) = .4 1019  20.8 1019 J
5000
E of 1 photon 2.48ev  2.48 1.6 1019 J  4 1019 J
Total ph.E 20.8 1019
= No. of photons =   5.2 photons
1 ph.E 4 1019
Monochromatic , Na lamp  5890 Ao () 5896 Ao
The total Energy of a monochromatic source E '  nhv(n  0,1, 2,......)
No. of photons  n  0,1, 2,......

n  E / s
'
' P
nE  [Link] photons emitted per second  
hv s hv  1240 
  (nm) 
 

Q. A m.c source of light emits light of   589nm find no. of photons emitted per
second. P = 40W
n P 40  6.25 1018 (eV )
   1.2 1018 photons per second
s 1240  (nm) 2.1(eV )
1eV  1.6 1019 J
1J  6.25 1018 eV

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Q. Find the no. of photons emitted in 1ms by a 5 milli Watt (mW) organ ion laser
emitting light of   4880 Ao
n P 5 103  6.25 1018
   12.5 1015 103  12.5 1012 photons/ms
s 12400 / 4880 2.5
 1.25 1013
1 sec = 12.5 x 1015 photons
1m sec
10 – 3 sec = ? photons
12.5 1015 103
 12.5 1012 ph / ms
1

SPECTROSCOPY
Bohr’s Theory Of Hydrogen Atom Postulates

1. Orbital Condition: for stationary orbits orbitat Angular

momentum
nh h
L  mvr  (or ) n (   1.05  10 34 J  S )
2 2
2. Frequency condition: An atom emits or absorbs a photon
of frequency v when an e  makes a transition between
two different Energy levels.
E1  E2  ze2 mv 2
V for absorption – E1 > E2 F  Bohr Expression for
h 4 o r 2 r
n 2 h 2 o 0.53 2 o
radii rn  rn  n A For Hydrogen r1  0.53 Ao  Bohr radius
 me ( ze)(e) z
h2 o r1 : r2 : r3 ......rn  1: 4 : 9.....n 2
r1 
 mc 2

Expression for Energy: An orbiting e  has both P.E and K.E

1 Ze(e)  Ze2 Ze2
Vn   ()ve  Force is attractive Kn 
4 o rn 4 o rn 8 o rn
 Ze 2
En  -ve  bound system energy . If E = + ve  is free system (unbound)
8 o rn
Vn : K n  2 :1
Total Eo numerically equal to K.E
K n  En

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Q. P.E. of an e  in an orbit is = - 27.2 eV. Find its kn and total Energy

27.2
Vn  27.2 eV Kn  eV  13.6eV En   Kn  13.6eV
2

K .E : P.E  1: 2  True for all central force system

P.E  2 K .E Earth – sun , Moon - earth

Electrostatic
Gravitation Conservative forces
M e e4 z 2
En   as n  outer e  s have greater Energies
8 o h n
2 2 2

 me ( ze)2 (e)2 mez 2e4

En   2 2 2
8 o2 h2 n2 8n h  o
me ( ze)2 (e) 2
Eg  ( n = 1)
8 02 h2
me e4 Z 2 13.6 Z 2
En   eV
8 o2 h2 n2 n2
Bohr’s theory not explained > Z = 1 (i.e other than Hydrogen ).Bohr ‘s theory Application
for Hydrogen and Hydrogen like atoms ( means having one e  ) i.e He + = - 13.6 x 4 ; eV
13.6
= - 54.4 eV For H  Z = 1  En  eV
n2

For H E  13.6eV n 6   0.38eV

1
13.6
n 2 E  3.4eV n 5   0.54eV
2 4
13.6
n 3 E  1.5eV n4   0.85eV
3 9
n 4 E  0.85eV n 3   1.5eV
4 16
n 5 E5  0.54eV n  2   3.4eV
25
n 6 E  0.38eV n 1   13.6eV
6 36
e can excite only from ground state not possible from excited to excited. But can de-
excite from any state to lower state in (so many [Link] ways)
nth level exite no. of photons emitted
n(n  1)
2

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Q. An e in ground state absorbs a photon of e 13.6eV and gets excitation . In de

excitation how many diff. photons get emitted .
5(5  1)
n5  10
2

Q. An e in ground state absorbs a photon of   938 Ao and get excited, how many
wavelengths come.
12400
E eV  13.2eV ● ● ●
938 5
E1  E2  13.6  13.2  0.4  0.38  n  6 4
6(6  1) 3
 15 2
2
 me Z 2 e 4  me Z 2 e 4
En1  En2 
8 02 h 2 n12 8 02 h 2 n22 1
hv  En2  En1

When e jumps from orbit n2 to orbit n1 , energy of the photon emitted hv  En  En  2 1

En2  En1 .me e 4 z 2 1 1 1 V me e 4 z 2  1 1 

V   2  2 V     
h 8 o2 h3  n1 n2   c 8 02 h3c  n12 n22 
Wave number  No. of waves in unit length = 1

1 1 1 me 4
V  Z 2 R  2  2  , R  2e 3 - Rydbergs constant = 1.097 x 107 / m = 10.97 x
  n1 n2  8 0 h c
106 m – 1 = 105 / cm R = dimensions – 1/Length = length – 1 R D  RH
 
Deuterium Hydrogen

Q. When an e  goes from n = 2 to n = 1 which of the following atoms give min.

wavelength?
1. H 2. He+ 3. Li+ + 4. Be+++
(Z = min 1) (z = max = 4)
1 1 1 1
 Z 2  Be+++  has min  For Hyd. Z = 1  V   R 2  2 
   n1 n2 
When we give extra amount of Energy than it requires the e  takes only certain amount
of en. and emits (gives off) extra energy as photon radiation  spectroscopic Transition
Excitation to next level by another electron  Auger effect
 Ze(e) n 2 h 2 o 0.53 n 2 o
F r   A  0.53n 2 Ao
4 o ro2 n
 me ze2 z
h2 o me4 z 2   Ze 2 Ze 2  ze 2 
 0.53 Ao En   n
V  , K .E  , E  
 me e 8 02 n 2 h 2 4 o rn 8 o rn 8 o rn 
2 n n

13.6z 2
eV
n2

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1 v me e 4 z 2  1 1  1 1 13.6 me4
V    2 3  2  2   Z 2R  2  2   eV  13.6 eV
 c 8 0 h c  n1 n2   n1 n2  n2 8 o2 h2
Ze2 m Z 2e4 4 2 n3h3
Vn  vn  e2 3 3 T 0 2 4
2nh o 4 0 n h me z e
Hydrogen Spectral Series:

1) Lyman Series  Lies in UV region

If n1 = 1, n2  2  Lyman. First line in any series has min E, and longest  last line in any
series ( has shortest ) is called series limit.
Longest wavelength
1 1 1  1 1 1  1
V   R    Shortest V   R   V  R
 12 2
2    1   
1
For Lyman Series : -    911.5 Ao  912 Ao (means n2 =  orbit ( e de exciting
R
from n orbit /state to lower)

2) Balmer Series : If n1 = 2 , n2  3  balmer series which lies in visible region.

1st line in Balmer Series - H (n  2, n  3)(3rd to 2)
1 2
1  1 1   1 1  5R
V H   R    R  
 H  22 2
3   4 9  36
36 36
H    912  6556.4  6566 Ao   6566 Ao
 5R 5 H
1  1 1  15  16
VH   R    R     4864 Ao
 H  22 2
4  16
  H
 15 R


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Series limit
1 R 1 o
V H   H  4   3646 A
H 4  R
 

3) Paschen Series: if n1 = 3, n2 ≥ 4  P.S lies in IR
1  1 1 R 9
V   R     
  32   9 R
16
4) Bracket Series : If n1 = 4, n2 ≥ 5  Bracket Series lies in FIR.  
R
5) P fund series : If n1 = 5, n2 ≥ 6  P fund series lies in FIR   25 / R
6) Humprey Series : If n1 = 6, n2 ≥ 7  Humprey series lies in FIR   36 / R

Series limit : Lyman Balmer Paschen Braket P fund Hump

1 4 9 16 25 36
 : : : : : :
R R R R R R
: 12 : 22 : 32 : 42 : 52 : 62
(1) (4) (9) (16) (25) (36) ( n12 )

Corrections:
me mn
Effective mass m*=
me  mn
me mn / mn me me
m* =  
 me  mn  / mn m
1 e 1
me
mn 1836me
1836me
m* =  0.999me
1837
m* <me (actually)
Bohr assumed mn  
me 1836
 Reduced mass m* = me is less than me, For Hyd. mH*   me  0.999me
me 1837
1
1836me
 RH < R  H >   The effect of considering the finite mass of nucleus is to
shift them towards longer wavelengths.
For Deufirium mn  2m p , mD  mH , RD  RH
(H – isotope) D  H

Successes:
1. It could explain H and H like atom
spectra
2. could correctly calculated
me 1 mp
   1836
mp 1836 me
3. Helped in the discovery of Deutrium 1H2

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Drawbacks:
1. Only H and H like spectra, couldnot explain spectra of many e  atoms
2. Relative intensity of spectral lines could not be explained
3. Fine structure of spectral lines
4. Stark and Zeeman effect
5. Adhoc usage of (mixing of) classical and Quantum theories L  mvr  n
 
Classical Quantum

Rydberg atoms: (special atoms)

1. Positronium: It is a bound state of e  positron pair ( e  - e  pair) resolving about their
common center of mass.
me me m e-
m*posi    e
m m 2 e+
1 e 1 e
mn me
n2 h2 o n 2 h 2 o
 rn  , All rn  rn  2   2  0.53 Ao
 me ze
2
 me ze2
Radii, Energy, values get doubled as compared to hydrogen values.
me z 2e4 13.6 / 2 6.8 R
 En  eV En pos  2 eV ,  posi  2H , R pos  H 2
8 0 n h
2 2 2
n 2
n
2. Muonic ‘H’ atom : Here an e  revolves around a nucleus meson of mass 207 me .
me 207
Effect mass m*   me  0.999me  mH*  me P 
me 208
1 
207 me
All values are similar to those of hydrogen . If a  meson of mass 207 me revolve
around a proton
mm 1836me  207 me + -
m*  1 2  m*  186me e
m1  m2 2043
All radii , energy and  values decreased by about 186 times as compared to Hydrogen
1 1 1 v e2 m z 2e4
atom. V  Time period T  n3 and V  3 ( v    ) v  e2 3 3
n n T 2 r 2nh 0 4 0 n h
Vector atom Model
Two salient features of vector atom model
1. Space quantization 2. Electron spin
With r to the dir. Of Ext. [Link] orbital planes of the e  can have some fixed

 
orientations only. Apart from orbital angular momentum L  e  possesses spin angular
 
 
momentum L s (intrinsic angular) such that the total angular momentum L j is the 
  
vector sum of the two L j  L  L s . Where L - [Link]
  
L - orbital [Link] Ls - spin [Link] L j = Total [Link]

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Quantum no. of e  (Quantum states of an e  )

[Link].- The no. of independent degrees of freedom (independent ways in which an
object/system acquires total energy.
1. Principle [Link]. : n = 1,2,3……
Denotes Total Energy and size of the orbit of e 
2. Orbital [Link]: ‘ℓ’ = 0,1,2,3 …. n – 1 (ℓ = 𝑛 − 1)  has n values

s P d f

Denotes orbital angular momentum L   (  1)  and shape of the orbital for in
 
S  L   0 in p orbital  L   2
3. Spin Q. No.: (s) (has only one value) s= ½  denotes intrinsic ang. Momentum
  3
L s  s  s  1  L s    0.866
2
4. Total angular momentum Q. No. (j)

j    s  denotes total angular momentum of e  as J   j ( j  1) 
1 1 1 3
Is never be negative  if ℓ = 1, 𝑠 = 2 → 𝑗 = 1 ± 2 = 2 , 2 values from   s to
1 1 1
  s   0, s   j  0   only s , j never be negative but ms , m j can be
2 2 2
negative
5. Magnetic orbital Q. no. (me ) : m  quantized

L z  m  m  denotes the z-component of L as L  z  me  , it is quantized and
can have integral values only from −ℓ … . . +ℓ i.e. 2ℓ + 1 values.

L
cos    z
Z, B

L
Lz  m 
m  Q
cos   
(  1) L

 m  (  1) cos 

6. Mag. Spin [Link].  ms  : Z,B

  1
2
It denotes the z component of L s as L sz  ms  Lsz

 ms  Q Ls
ms can have 2s+1 values

 
Q
from +s to –s ms  1 , 1 Lsz  ms 
2 2
L ms  ms  12 
cos   sz  
L s( s  1) s ( s  1)

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1  1 
ms  s ( s  1) cos  cos   2  1   cos 1  
3 3  3
2
  125.7o (or ) 54.3o

7.    
[Link] angular [Link].: L j -It denotes Z-component of L j as L jz  mj 


It (mj) can have values from  j to j  2 j  1 values L jz  m j 
Ljz mj  mj
cos     
Lj j  j  1 j ( j  1)
Z, B
mj  j ( j  1) cos 
Lz  m j 
1 1 3
For   1, s  j s  , Q
2 2 2 
Lj
3 3 3 3 1 1 3
For j   mj  to  , , ,
2 2 2 2 2 2 2
3 1 1 3
L jz  , , , 
2 2 2 2

Magnetic Dipole moments of the Electron

ne
i  q/t   ve . An orbiting e  is equivalent to a tiny current loop and hence produces
t
a [Link] at the center. Dipole moment   iA  veA Z,B

 3
 1 v v Ver eVr 2

  ve r 2  v      e r 2  
 T s 2 r  1
2 2 2

 eVr m
  
2 m  1
2
 e e 
   mvr.  L (e - charge of e   ve )  3
2

2m 2m
   
e 
 
2m
L 
 , L opposite in direction -ve sign L

 e 
ve indicates direction. Magnetic dipole moment    L 
2m
 m
 e
Gyromag. Ratio of     Am 2 or J / T
L 2 m
 e e
Quantum     (  1)  (  1)
2m 2m
eh e 
Bohr magneton  B  9.24 1024 J / T ,    .B (  1)
4 m 2m

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Spin dipole moment

 e 
Spin dipole – assigned a value  s  2 Ls
2m
 e e eK 3 
s  2 s( s  1) 2 s ( s  1)  2  s  3B
2m 2m 2m 2

s e
   Gyremag n e due to spin ratio of  Gyromag ratio for spin is double that
Ls m

 e
of orbital motion spin In general g g  Lande splitting factor g = 1 for
L 2m
orbital motion g = 2 for spin  spin is more imp than orbital motion in magnetism
s  
cos    z s   s cos   s   1  3B   1  s2   B
s z
 3  3

Spin – orbit interaction

The orbital motion of e effects its spin motion and  B B
splits every electronic energy level into two
components. But for s orbit The E. diff. between two E
levels is 2B B but for s-orbital ,L=O – No splitting s-
B B
level is always a [Link] structure of spectral line
is due to spin orbit interaction. E '  E  B B
Coupling Schemes
They are two types
1. L.S (Russel – sanders) coupling 2. j – j coupling
1. L - S coupling
       S1
1
J  L  S  has values from L  S to L  S
L
4
L  1   2   3  ....... n    i , J
1 i S
S  s1  s2  ..... si 2
S2
Due to strong electric dipole (residual

Electrostatic) interaction 1 ,  2 ,  3 etc. vectors couple to give L i.e L  1   2  .....   i
Due to strong spin spin correlation s1 , s2 , s3 ..... etc. vectors of individuals e s couple to
  
give S i.e. S  s1  s2  s3 ..... si . These resultant L and S couple weakly to give resultant
J of the entire [Link] when , s interaction is weak L – S coupling is observed in
atoms. It observed mostly in lighter atoms.
2. J-J coupling
Here due to strong spin orbit interaction i, si vectors of individual e couple first to give
ji . The ji vector couple next to give resultant J i.e. has values from J  j1  j2  j3 ......   ji
j1  j2 to j1  j2 This mostly observed in heavy atoms.

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Selection rules in L-S coupling:

One e many e
L = ± 1 L=0,±1
S = 0 S = 0
J = 0, ±1 J = 0, ±1
n = Unrestricted
Intensity Rules
L = - 1, J = - 1  highest intensity strongest light
L = - 1, J = 0  high intensity
L = +1 , J = +1  Weak intensity
L = +1 , J = 0  weakest intensity
L = +1 , J = -1
Forbidden transition
L = -1 , J = +1

Spectral Notation (it is for L-S coupling only)

n (281) ( SPDF ) J - complete spectral Notation doublet
e.g: Na – 11  1s 2s 2p 3s
2 2 6 1

n=3 3 2S 1/2
s= ½ , 2s + 1 = 2
ℓ =L=0
J=O½=+½ Ground state
 Li – s 1s2 2s1
 H – 1  1s1
n = 2,
ℓ=L=0
s = ½  2s + 1 = 2, J = ½ 2 2S ½
Similarly for ‘H’ also Ground state is 12S1/2  The Gr. State spectral for Alkali atoms is
n2S1/2
Fine structure of Na D lines (D – doublet)
Ground state term is 2S1/2
For upper P-state  L = 1 (p – orbital)
S = ½ 2s+1-2
J = 1  ½ = ½, 3/2
2P1/2  S1/2 D1 =  = 5896 Ao  L = - 1
2

s = 0
J = 0 intensity is high
2P3/2  S1/2 D2 =  = 5890 A  L = - 1
2 o

s = 0
J = -1 intensity is highest
D1 : D2
Intensity
1 : 2

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We take J value 2s
If L < S  2L + 1 i.e J = S < L  2s + 1 So here J = ½ only another state is not possible
In the absence of [Link] S L = 0 but in presence it may split
2
P3/2  2P1/2 not possible P  S  principle series
Main reason for D1 , D2 is due to splitting of P- levels.- Split is due to spin – orbit
interaction Many e  spectra :
No. of e  in nth orbit is – n2 without spin Spin degeneracy = 2s + 1
2n – with spin
2

(2s + 1) n2
In nature if n = 4 only allowed the no. of elements would be
n=1 : 2e 
n=2 : 8e 
n=3 : 18e 
n=4 : 32e 
Z = 60 element possible
 Min. [Link]. of e  = 4  n,ℓ, m,s.
 How many wave functions for one energy that much degeneracy take place.
Similarly [Link]
e.g : 2P  ℓ = 1 , n = 2  2ℓ + 1 = 3
2ℓ + 1  ℓ. Degeneracy  -1,0, +1

Wave function  nme   211 ,  210 ,  21

3 fold degeneracy without spin
(2ℓ + 1)  without spin
Total degeneracy (2ℓ + 1) (2s + 1)  with spin
2(2  1) or (2 j  1)
e.g.: ℓ = 2  2ℓ + 1 = 5
n=3
+2 +1 0 -1 -2
↿⇂ ↿⇂ ↿⇂ ↿⇂ ↿⇂

 322  321  320  321  322

The 4 –[Link].s to specify an e  in an atom are n, ℓ, me , ms . If different [Link] have
same energy they are said to be degenerate.
ℓ - degeneracy is 2ℓ + 1  2ℓ + 1 fold degeneracy.
S – degeneracy is 2s + 1  2s + 1 fold degeneracy
 Total degeneracy is (2s + 1) (2ℓ + 1) = 2 (2ℓ + 1)
i.e. 2 (2ℓ + 1) fold degeneracy
* If n,ℓ are same they are called equivalent e  s. If n , ℓ are different they are called non-
equivalent e  .

Spectral terms for non-equivalent e Spectral terms for 3p, 3d

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Sp 3d
n=3 n=3
ℓ=1 ℓ = 2 (non – equivalent e  )
s =½ s=½
F D P
L  1   2 to 1   2  3 to 1
i.e. 3 2 1
S  s1  s2 to s1  s2  1 to 0
 
Triplet singlet
states state

Selection rules: (order is important) (first s, next l, next J)

1. The state with highest S will have lowest energy

2. State with highest ‘L’ will have lowest energy
3. State with lowest ‘J’ will have lowest energy

J  L  S to L  S No. of possible spectral terms = 12

1 1 1 3 3
P1 , D2 , F3 , P0,1,2 , D1,2,3 , 3F2,3,4 which is [Link] term
Highest S  1 (simply multiplicity is high 2s + 1 = 3, S = 1)
Highest L  3  F
Lowest J  2   3 F2
Possible spectral terms and identify G.S term for 4d , 4f
Individual e  S, P, D, F, G, H, O
4d 4f ℓ = 0, 1 , 2 , 3 , 4 , 5 , 6
n=4 n=4
ℓ=2 ℓ=3
s=½ s=½
Total atom
L = 5,4,3,2,1
HGFDP
S = 1, 0

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Singlet  S = 0, L=1,2,3,4,5 S = 0, L =1  J = 2  1P1

S = 0, L = 2  J = 2 1D2
Triplet  S = 1, L = 1,2,3,4,5
S
L 1 2 3 4 5
0,1,2 1,2,3 2,3,4 3,4,5 4,5,6
3P 3H
0,1,2 3F 4,5,6
2,3,4
2s+1=3
3D
1,2,3 3G
3,4,5

S = 0, L = 3  J = 3  1F3
L = 4  J = 4 1G4
L = 5  J = 5  1H5
Ground state  3 H4
Spectral terms for 3s,3p,3d
3s 3p 3d
n=3 n=3 n=3
1  0 2  1 3  2
S1  1 2 S2  1 2 S3  1 2
G.S  S. high L, low J
Quadralet
L = 1,2,3, S =3/2
For S = 3/2 , L = 3 J  L  S to L  S  3 2  3 to 3  3 2
J= 9
2
7
2
5
2
3
2  4 F12 ,7 2, 5 2, 3 2
G.S  4 F3 2
Equivalent Electrons : (n , ℓ values same)

1𝑆 2 ↿⇂ -1 0 +1 2𝑃6
↿⇂ ↿⇂ ↿⇂
n=2 2 2
 =1 1 1
m  2  1   2 1  1  3 i.e. -1 , 0 , +1  ms  (should) differ
Here n ,  are same  m or ms must differ. Here for a comp[lately filled subshell L =
0 , S = 0, J = O  The only term possible is 1 S 0 . For half filled subshells the G.S is ↿ S1
 2S1/2
 1
↿ ↿ ↿ P  ↿ ↿ ↿ P  S 3 2 Quartet
3 3 4

S 21

↿ ↿ ↿ ↿ ↿

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m  1 0 1
d 5  6 S5 2 Hextet
ms 1
2
1
2
1
2

↿ ↿ ↿ ↿ ↿ ↿ ↿ f 7  8 S7 2 Octet

L m   1  0  1  0 
 J  32 2s  1  4  4 S 3 2
S  m s
1  1  1  3
2 2 2 2 
The terms for  n  are same as those of  n 
mr
(m-max . no. of e  in the orbital)
r

Spectral terms same but G.S. different Terms for P2 are same as P4
 n   n 
r mr
d3 - d7
P1 - P5 d4 - d6
P2 - P4
d1 - d9
d2 - d8
For less than half filled case normal order is valid
Highest S – lowest E
Highest L – lowest E
Lowest J – lowest E
For more than half filled case inverted order prevails i.e.
Highest S - lowest E
Highest L – lowest E
Highest J – lowest Energy
For carbon Z = 6. 1s 2 2 s 2 2 p 2 less than half filled → G.s is 3P0
Oxygen Z = 8 1s 2 2 s 2 2 p 4 more than half filled → G.s is 3P2
Both atoms have same spectral terms
1
S0 , 1 D2 , 3 P0 , 3 P1 , 3 P2 Spectral terms same for C & O but G. states different
In Carbon – Normal order  G.s – 3P0
In Oxygen – Inverted order i.e, G.s – 3P2
L - S Interaction Energy
            
E , s   L.S   J LS J .J  L.L  S .S  2 L.S
    1 2
J 2  L2  S 2  2 L.S L.S   J  L2  S 2 
2
2
  J  J  1  L  L  1  S  S  1 
2 
   2
 L.S    2 
 J  J  1  L  L  1  S  S  1 

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Lande’s Interval Rule J J+1 J+2 J+3

The energy difference between two levels in a fine structure
multiple is proportional to higher J i.e. J+1. Consider two
successive levels J & J+1, the energy interval between these
two levels
E  EJ 1  EJ    J  1 J  2   J  J  1 
i.e   2  J  1 or   J  1 Difference  J + 1

E J 1 next higher level to J 

In a triplet state the wave number interval is found to be 20 J+2
90cm- 1
cm-1 and 40 cm-1, there is a higher state with interval 22 cm-
1
and 33 cm-1, find the no. of allowed transitions possible J+1
between these two states 20cm- 1
In the lower state let J levels be J, J+1, J+2 J
E  EJ 1  EJ  J  1 i.e. 20
J  1 1 20

J  2 40 2
J  2 i.e. 40 2  J  1  J  2
J  1 20
 J 0 J=0
J  2 40
 J , J  1, J  2  0,1, 2 S  LS
S  1 triplet  , J  L  S, L  1 J  LS
3
P0 , 3 P1 , 3 P2 2  L 1  L  1
2
J  1 22 S  1, J  L  3, L  2
  3J  3  2 J  4  J  1
1. J  2 33 3 3
D1 , 3 D2 , 3 D3
J , J  1, J  2  1, 2,3

6 – possible transitions
L  0, 1

 S  0
J  0, 1

J0  0 
Many e  Because S = 1 triplet Sinble e  S – only S  1 doublete
2
3) J –j coupling
1. Here L, S are no longer valid
2. Parity of the configurat must change in
An electric dipole transition (even  odd) is called Laporte’s rule

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Laporte’s rule
Parity of the configuration must change in an electric dipole transition (even  odd)
electric dipole trans must change
L = 0 – (even) parity
L = 2 - odd parity
∆L = ±1 this is for 1 e  only not for > 1 e 
 If two e  jump at sametime 
   if only e  jump at a time
 first e 1   1 
 2nd e   0,  2   L  1
 2 

3. J  O, 1 (J0→0 is forbidden transition) Unpertabed level disturbance

L  1, 2, 3

1
P P1

S 0 1
D2
D

1
F F3

3 P 3d
3
P0
P 3
P1
3
P2
Spin – Spin S 1 D 3
D1
Interaction 3
D2
(s - s) 3
D3
3
F F2
Electric dipole 3
F3
(   ) 3
F4
Spin orbit int.

Total 12 terms Low J → low energy (L-S)

For j – j 3p, 3d
1  1,  2  2 s1  1 2 , s2  1 2 j1   1 2 , s 2  , j2   3 2 , 5 2 

Possible combinations  1 2 , 3 2  ,  1 2 , 5 2  ,  3 2 , 3 2  ,  3 2 , 5 2 
J values J = 1,2
J = 2,3
J=0,1,2,3 Total 12 terms
J=1,2,3,4 Max. Energy for max. J
Minimum Energy for min J

Larmor’s theorem
The effect of external [Link] applied on an orbiting
 e  is to make the entire orbit
precise such that the L sweeps a cone around B . The change in the orbital angular
eB
frequency or precisional angular vel. wP  w  
2m

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e
 1.76 1011 rad / sec
m

1. When a [Link] of 2T is applied to an atom, find the change in an its orbital

ang. Frequency.
e e 1.6  10 19 c
WP = ∆w=± 2   31
 1.76 1011 radian / sec
2m m 9.110 kg
w  eB
Precisional frequency  w  2 v  v p  
2 4 m

Zeeman Effect
Splitting of spectral line in an ext.
[Link] is called Zeeman effect. It is a
magneto optical phenomenon.
In a strong field each line splits into three
components it is called Normal Zeeman
effect which could be explained by classical
physics also.
In a weak field if each line splits into more
than 3 componnets, is called Anamolus
Zeeman effect. This could be explained only
by Quantum mechanics.

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In longitual view only two components are observed and both are circularly polarized. In
transverse view and components are observed all are plane polarized. Normal Zeeman
Effect – Lorentz classical Explaination is based on Larmous precision.
eB  2 dv  Be 2 e  Be 2
dv  dv   ratio was estimated. d  
4 m c 4 mc m 4 xmc

Q.: When 2T field is applied on a monochromatic source emitting   5890 Ao . Find

Zeeman shift.
 Be 2 2 1.76 1011  (5890 1010 ) 2 1.76  346921102 1011 1020
d   
4 mc 4  3  3 108 3  3.14 108
346921 59 1.8  59 109 102
  107  108   3481101
2  3  3 108

Normal Zeeman Effect

Quantum mechanical Expression:
Debye explained normal Zeeman effect without
considering e  spin . S  0 Here e  has only
orbital dipole moment  
 e 
  L     B e    1
2m
When a strong M.F is applied the interaction energy between   and B is
e
E     .B (    (  1)    B (  1) E   B B (  1) cos 
2m
E  B Bm E  g  mB Bm .As m can have 2  1 values each ‘  ’ state splits into
2  1 sublevels in a strong field. For lower level E  B Bm . Higher level E '   B Bm'
E  E ' E   B B(m2  m ) i.e B B m . Selection rules for m are
m  0 , 1 E  B Bm
 
 components  components
parallel perpendicular

E ehB eB eB
v    m v 
 m v  0, 
h h  4 m 4 m 4 m
eB eB
If m  0  v  0 m  1  v  m  1  v 
4 m 4 m
Thus Q,M explains normal Zeeman effect based on  degeneracy

Anomalus Zeeman Effect

This cannt be explained without considering e  spin S  O
 e  e
  (  1)    B (  1)  s  2 s(s  1)   2  B s(s  1)
2m 2m

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Due to the addition 2 factor in  s the resultant  j is not exactly antiparallel to J.

Considering only the parallel components  j   cos(, j )  s cos( s, j ) .

On solving →  j   g J ( J  1)  B → g - lande g splitting factor . In a weak field

E    j .B
=  g  B B J ( J  1) cos 
(if applied B <[Link] Energy – Anomalous (weak field).
If B > mag. Inter energy (  - s) – Normal (strong field)

E  g  B Bmj e mj  0, 1
B  Selection rules for
E  g  B Bmj 2 m
 1 v hv E  E g eh B m j geB
In term of wave no. v     v    mj
 c hc hc hc 4 mhc 4 cm

 
v  gL' mj cm1 L 
eB
4 mc
 Lorentz unit As mj can have 2j + 1 values , in a
weak field each j level splits into 2j + 1 sublevels to give anamalus Zeeman pattern of
more than 3 components . In wave no. terms v  gL ' mj
Selection rules for mj are mj  0, 1
eB
L'  em 1 Here g – Lande’s splitting factor
4 mc
J ( J  1)  s( s  1)  L( L  1)
g  1
2 J ( J  1)
g - denotes the separation between lines
g L denotes the separation between wave no.
No. of Zeeman levels are either (2s+1) (2L+1) or 2J+1
Anamalus Zeeman effect of Na , D1 , D2 lines
In a weak field D1 line splits into 4 components  2 , 2  D2 line splits into 6
components  2 , 4 

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J ( J  1)  S (S 1)  L(L 1)
g  1
2 ( J  1)

1. For 2 P3 2  S  1 2 g  1
3
2  5 / 2   12  3 / 2   1(2)
 3  1
L=1
J = 3/2
2. 15 3
 2
10 10 g  43
 1 4 4  1  1  10
15
4 2  15 30

1  12  3 2   12  3 2   0 1 64
2. For 2 S 12  S  1 2 g   11  2
2 12  3 2  6
4

L=0
J = 12
2(3)  1(2)  2(3)
3. For 3
D2  S  1 g  1  1  16  7 6
2(2)(3)
L=2
J=2
1  5 2  7 2   12  3 2   2(3) 14 6
4. For 2 D5 2  S  1 2 g  1 
2 5
2  2 
7 70 5
L=2
J = 52
1  1 2  3 2   1 2  3 2   1(2) 2 2
5. For 2 P12  S  1 2 g  1 
2  1 2  3 2  6 3

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Q. Show that g = 1 for orbital motion and g = 2 for spin

J  J  1  J  J  1
For orbital motion S = 0, J = L  g  1 
2 J  J  1
J  J  1  J  J  1
For spin L = 0, J = S  g = 1 + g  1
2 J  J  1

Paschen – Back Effect

When the M.F B value is gradually reduced. After a specific B the anomalous Zeeman
pattern of more than 3 – components transforms into Normal Zeeman triplet either by
disappearance or merger of some lines. In a weak field due to L – S coupling J is formed

which precises about B giving anamolous pattern. In a strong field L- S coupling breaks
down J doesn’t exist. L,S separately precise about B. Here this strong field [Link].
m  2ms comes. Selection rules   m  2ms   0, 1 as m  0, 1 . ms  0
When spin exists Anam Z.E observed in weak field and Normal Z.E = in strong filed
when spin doesnot exist – only N Z E . No. of paschen back levels =  2 S  1 2 L  1
When spin exists Ana. Pattern observed. If spin doesnot exist only Normal Zeeman effect
is observed.
e.g.
1. 3 D3 3 P2 is a triplet-triplet transition (S – 1) Hence Anam Z.E
2. 2
P3 2 2 S2 2 is doublet – doublet transition (S = ½ ) Anam Z. E
3. 1
P1 1 S0 is singlet – singlet transition (S = 0)  Normal Z.E
Q. Normal Zeeman Effect can be observed in atoms with
a) Even [Link] e  s only b) Odd no. of e  s only c) Any [Link] e  s only d) None
Stark Effect
It is an electro – optical phenomenon . Splitting of spectral lines in powerful E.F’s of the
order of 105 volt / cm is called stark effect.
 Stark splitting is a pattern of symmetrical lines depending on the principle [Link]. ‘n’
 The no. of lines and width of the spectrum increases with mg ‘n’ i.e. splitting for
H lines will be more (both in no, and width) then H  The splitting is in the
multiples of a unit and is proportional to the applied E.F. ‘F’
 If the splitting is  F  is called linear (or) 1 st order stark effect
Which occurs only in ‘H’ like atoms and for smaller ‘n’
 For higher ‘n’ and other atoms the splitting is  F2  is called 2nd order (or)
quadratic stark effect. Which is extremely weak.
In weak field L-S coupling holds good and fine structure splitting dominates stark
splitting .Therefore Weak field stark effect can never be observed . In a strong  field
L – S coupling break down only perpendicular presises around the applied F (spin is
unaffected by E.F)

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3ao e
After application of the filed , Energy E  E0  Fn(n2  n1 )
2z
E E0  E 3a0 e
v    Fn(n2  n1 )cm 1 Here ao - Bohr’s radius n – Principle
hc hc 2 zhc
[Link]. n1 , n2 - new [Link]. in parabolic coordinates m  n  n2  n1  1 If F is in Volt / cm
6.4 105
v  Fn(n2  n1 )
Z
n  1, 2,3,...... m  0, 1, 2....(n  1) n1  0,1, 2,....upto (n  1)
n2  0,1, 2,....upto (n 1)

Therefore in strong field H - line splits into 8  7 , a total of 15 components. In

Zeeman effect [Link] lifts the degeneracy completely. Whereas in stark eff.
[Link] lifts the degeneracy partially.  Mag. Filed is preferable to lift degeneracy For
the G.S of ‘H’ atom 1st order stark effect is [Link] to Q.M ‘H’ atom in excited
state (behaves like a electric dipole). The interaction Energy between the dipole and the
field is  E '   .F  erF cos  . This is considered as the perturbation term H ' over
the uperturbed Hamiltonian (total Energy ).  2 e2 According to Q.M 1st order stark

2m r
effect is zero for any non-degenerate state. As G.S of ‘H’ atom is non-degenerate here
also 1st order stark effect is ‘O’ But 2 nd order stark effect for [Link] ‘H’ atom is 
9 3 2
a0 F But n = 2 state of ‘H’ is 4 – fold degenerate (n2) , they are
4
1200 > , 1210 > , 1211 > 121-1 >
2S 2P
-1 0 +1

 nm  200  211  210  211

New notation nm  | 200  | 21  1  | 210  | 211 
Detailed calculations show only 1211> , 121-1> are unaffected

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Wave f sn

‘H’ atom in 1st excited state has a permanent [Link] of 3a0 e .

Hyper fine Structure of spectral lines

hfs – structure .The components of the fine structure are found to be a bunch of very
closely spaced lines ( the separation 1cm -1)
This hfs structure is due to 2 nuclear properties
1. Isotope effect
2. Nuclear magnetic moment
1 1 1
Isotope effect: ‘H’ has an isotope Deutirium – 1 H 2   RH  2  2 
H  n n2 
As RD  RH slightly, D  H slightly for H line it is
 1.79 Ao For H  line  1.33 Ao . Nuclear magnetic
moment: Even for single isotopes like Bismuth – 4722 Ao
6 hfs – components are observed . Pauli attributed this to
nuclear spin.

I  I ( I  1)  I  Nuclear spin [Link]

I  Nuclear spin angular momentum
 e 
Similar to e     g (  1)  Nuclear spin dipole moment is
 2m 
 e e
 I  gI I ( I  1) Nuclear g – factor  N   5.05 10 27 J / T
2mp 2mp
e
B   9.27 1027 J / T . Here mI can have 2 I  1 values from  I ....to....  I Z –
2me
component of spin – dipole moment  I z  g I  N mI As max. possible value of mI is
I   I z  g I  N I This is called Nucleus spin-dipole moment .The total angular
       
momentum for the entire atom F  L  S  I F  J  I F  F ( F  1)  F is
called hfs [Link]. and can have values from J  I to J  I If J  I , F can have 2 J  1
values If J  I , F can have 2 I  1 values. Landes interval rule is applicable here also,
i.e. the energy between any 2 successive hfs components is proportional to F + 1 i.e. hiher
‘F’ . Selection rules for hfs [Link]. are F  0, 1 Hfs of Na D2 line

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for Na D2 lines is 2 P3 J  3 2 I  3 2 F  0,1, 2,3

2

For lower 2
S 12 J  1
2 I  32 F = 1 , 2
Though 6 –possible components are there only 2-componets are well resolved.
For Bi – 4722Ao line  for upper level J  1 2 I  9 2 F 4 , 5
For lower level J  3 2 I  9 2 F = 3,4,5,6 . All 6 components are well resolved
Alkali spectrum: (valence e  is ns1  one e  spectra)
R
From Bohrs theory wave [Link] of alkali atoms can be written as v  v 
n2
The spectra of alkali atoms are found to consists of 4-series.
1. Most persistent and intense called principle series (P  S)
2. A series of sharp lines called sharp series (S  P)
3. A bunch of somewhat diffused lines called diffused series (d  p)
4. Fundamental or Bergmen series (IR region) (f  d)
R
vmP  vP  , m  2,3....
m  P
2

R
vms  vs  , m  2,3....
m  S 
2

R
vmd  vd  , m  3, 4....
m  d 
2

R
vmf  vf  , m  4,5....
  m  f 
2

fixed term
 
Running term

Fixed term of principle series is equal to a Running term of sharp series with m = 1 i.e.
R
vP 
(1  s)2
The fixed term of sharp and different series are equal to the 1 st running term of principle
series
R
2 
vs  vd  m  2
2  P
The fixed term of Fundamental series is equal to the 1st running term of different series. i.e
R R R
vf  (m  3)  We get vmp   , m = 2,3,….
3  d  1  s   m  P 
2 2 2

R R
vms   , m  2,3...
2  p m  s
2 1

R R R R
vmd   , m  3, 4... vmf   , m  4,5...
2  p m  d  3  d  m  f 
2 2 2 2

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Rydberg Schuster’s Law: Range’s Law:

The difference between fixed terms of The difference between fixed terms of
principle and sharp or diffuse series is diffuse and fund series is equal to the 1 st
equal to the 1st frequency term of principle frequency term of diffuse series.
series. i.e. vp  vs ( or ) d  v2p i.e. vd  vf  v3d
R R R R
v2p    v2p   v3d
1  s   2  P  2  P 3  d 
2 2 2

The observed series in emission spectrum arises from following transitions

In Na atom the 4 transitions can be designated as
Principle series np  ns n>2
Sharp series ns  np n>3
Diffuse series nd  np n>2
Fundamental series nf  nd n>3
The only resonance line is possible in Na is 3s  3p (3p  3s)
Spectrum of Helium Atom:
Two identical particles like 2e  in an atom (or) 2pro (or) 2neutrons inside the nucleus
have a special interaction called spin – exchange interaction whose sign depends on the
relative orientation of their spin.
When 2e  have  - parallel spins (S = 1 - ortho) they behave as if they repel each
other and get farther.
When the spins are ↿⇂ - anti parallel (s = o , para) they behave as if they attract each other
and get closer.
For symm. Wave function 12   21
Antisymm wave function 12   21
Consider 2 different states 1 and 2 with 2 identical particles
The proper description of the system is
1
 1 (a) 2 (b)   2 (a)1 (b)  Symmetric
2
1
 1 (a) 2 (b)   2 (a)1 (b)  Antisym
2
Bosens have – symmetric wave function
Fermions have – Antisym wave function
The total wave function for fermions must be antisymmetric


=
Spin wave function
Space wave function
For Triplet states (S=1) , Ortho-helium

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   spin wave functions are symmetric   must be antisymmetric This leads to Pauli’s
exclusion principle. For singlet state (S=O) , para – helium  is antisymmetric   -
must be symmetric i.e. two fermions with antiparallel spins only can exist in same energy
[Link] ground state of He = 1 1 S 0 The 1st excited state in Para helium is = 2s state
with S = 0, L = 0 , J = 0 i.e. 21 S 0 . In ortho helium (↿↾) 1st excited state - 23 S1  ↿↾ S
= 1, L = 0, J = 1. G.S for para He. Is possible (singlet G.S) but. G.S for ortho He is
 
impossible 23 S1 .As 1s  2s transition is forbidden He atom can be excited only by
non- spectroscopic transition 1st exci. State of para He - 21 S 0 is meta stable because
  1 is violated 1st exci. State in ortho helium 23 S1 is highly meta stable because S
= 0 , L =  1 both get [Link] Hamiltonian for He atom Ho = - 2z2 EH = 108.9 eV
but the observed total E is = - 78.9 eV only  Perturbation must be [Link]
5
repulsion between the 2 e  s becomes the perturbation term it is ZEH
4
5 5
 H 1  zEH  H  H o  H 1  2 z 2 EH  zE4  75eV
4 4
Hence variation method is more suitable But perturbation theory gives better and better
results for Higher ‘z’ atoms like Li+, Be++, B+++,C++++

X-ray Spectra
X-rays  Rontgen

When e  s of high K.E (velocity) go and fall on a

target of high atomic weight and melting point x-ray
are produced.
I vs  graph is as shown

1. For every acceleration p.d there is a sharp min x-rays of all possible wavelengths are
present continuously .  It is called continous (or) white x – ray spectrum.
2. As accel. Pd V  ses min shifts towards shorter wavelength
1
i.e. min  Duant Hunt Rule
v
3. Above a specific acc. ling p.d , depending on the nature of the target 2 or 3 sharp
peaks superimposed on the continuous spectrum is observed. These lines are called
characteristic d-rays.

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Origin of Continous X-Rays

The energy lost by the e  s in the strong Electrostatic field of nucleus gets converted into
photons energy (inverse photo electric effect) When e  loses its entire energy eV we get
max energy photon or min
hc hc 12400 o 1 12400 o
i.e eV  hv  min   A i.e min  min  A
min eV V v v

Origin of characteristic x-rays :

K  K   K L  L  L M  M  K  L  M

Thus characteristic x-rays are due to inner electronic transition.

K - line is a doublet due to spin – orbit interaction in 2p level

Continuous x – rays also known as Braking radiation or

Bremmstraulum x-rays

Mosleys Law
States in character x-rays v  z or v  a ( z  b)
3
a – comes from Bohr’s theorey  RC
2
b = screening constant b = 1 for K lines of any element b= 7.5 for L lines of any
element
Q. For an atom with z = 29 , K  1.5 Ao for what z , K  is equal to 0.75 Ao.
C c
v  a ( z  1) ,  a ( z  b)  a ( z  1)
1 2

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1 a(29  1)  1   28 
2

=  =    0.75
2 a( z  1)  2   Z 21
2

2  z2  1 28 1 z  1 1 z2  1
    2    z2  1  28 1.4  39.2 = z2  40
1 28 z2  1 2 28 4 28.28

Q. For Uranium K  0.72 Ao for which element K  2.16 Ao

c
U  z1  92, 1  0.72 Ao v  a ( z  1)  a (92  1)
92
1
c
z2  ? 2  2.16 Ao  a ( z  1)
2
c
1 2 a (91) 2.16 3 91 910
     1.7( z  1)  91 z  1  z  54
c
2 1 a( z  1) 0.72 z 1 17

ESR spectrum (Electron – spin resonance / EPR - e  paramagnetic

Resonance )
It is a technique confined to the study of
molecules or ions having unpaired e  spin
 e
 s  g 8( s  1)   g  B s ( s  1)
2m
([Link] dipole moment)
E  s .B  g B Bms (In an ext [Link]
B interaction energy E)
ms  2 s  1  2  1 2   1  2 values ,  1 2
the [Link] splits
1 1
In 2 sublevels 1. E 12  g  B B (ms  1 2 ) 2. E 12  g  B B (ms  1 2 )
2 2
Inducing a transition between these two sublevels by EM radiation of energy hv  g B B
is the principle of ESR absorption. If the [Link] of the radiation is perpendicular to the
applied filed reorientation of  s vector takes place resonance absorption [Link]
values of frequencies of EM radiation lie in Microwave region. Atoms with unpaired e 
like , H, N , etc…. molecules like NO 2, NO, etc….., transition metal ions like Cu, free
radicals like OH  , rare earth elememts can be studied by the ESR Resonance. Fine
structure of ESR: This is because of the interaction between e  spin dipole moment  s
and Nuclear mag. Moment  I z If nuclear spin I  O (e.g. C – 6) fine structure is absent.
If I  1 2 each ms level splits into 2 I  1 sublevels.

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Consider a nucleus with I  1

2 , mI can have 2 I  1 values form  I to  I i.e.  1 2
Each ms level splits into, 2 I  1 sublevels, selection rules in ESR spectrum are
ms  1, mI  0  We get 2 I  1 components in fine structure.

Q. Sketch ESR fine structure for an unpaired e  in a nucleus with I  1

I  1  M I  2I  1  2(1)  1  3  1,0,1

Q. In ESR resonance absorption B = 1.3 T and a = 35 Giga Hetz find spin – g factor
E  hv  g B B
hv 6.625 1034  35 109 66 35
g  Hertz    10  10 1  1.76 /1.87
B B 24
9.27 10 1.3 93 18
Exactly – 1.924 for g (donot take approxi while solving for g)

Q. A free e  gives resonance at 9.3 GHz what is the B value if g = 2.0023

hv 6.625 1034  9.3 109 Hz
hv  g  B B  B  
g B 2.0023  9.27 1024 J / T
 3.3 101  0.33 Tesla (can take approximations while solving for other than g)
If there are n-equivalent nuclei with same spin I we get (2nI  1)
If there are n – equivalent nuceii with spin I i each and m-equivalent nuclei with spins I j

each we get  2nI i  1 2nI j  1 lines. 
If there are n – different nuclei with different spins I1 , I 2 ,....I n then we get
 2 I1  1 2 I 2  1 .....  2 I n  1 lines If I1  I 2  I 3  ....  I 0 then we get  2 I  1 lines
n

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Q. If an unpaired e  interacts with 4 – different nuclei each having spin I  1

2 the ESR
fine structure component are

 2I  1   2  1 2   1   24  16 components
4

Nuclear spin interacts with e  mag. dipole Moment in 2 ways

1. Dipole – dipole interaction
2. Fermi contact interaction

LASERS
At thermal equilibrium N1  N2 The rate of Absorption / probability
dN12
E2  E1  hv  B12 N1   v21 
dt
1. Induced stimulated absorption

2. Spontaneous emission Eienstein coefficient of induced absorption

The rate of emission

dN 21
 A21 N 2
dt sp 
Eienst .coefficient
of spon tan eous emission

dN12
3. Stimulated emission  B21 N 2   v21 
dt st 
Eienst .coefficient
of stimulated emission

B12
 1.  Induced / Absorption probability  stimulated emission probability
B21
A21 8 hv3 A
  21  v3  i.e E 3   E2  E1 
3
3
B21 c B21

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i.e As the Energy different between 2 levels increases spontaneous emission dominates
over stimulated emission we cannot control spot emission but can control stimulated
emits Laser light

Laser light

Same  and in phase uni direction

 Light emitted by stimulated emission is monochromatic and also coherent
(same/constant phase different )
 For stimulated emission to occur N2 >> N1 is called Population inversion . In
which population inversion is achieved is called as an active system .
 The process of achieving [Link]. is called
Pumping:

1. Optical Pumping (Ruby Laser)

2. Pumping by inelastic atomic collisions (Electric discharge)
3. Direct Electrical pumping this is used in semi conductor laser
4. Chemical pumping (HF laser)
Thermal pumping is not possible
Stimulated emmi. Gain coefficient is proportional to N 2  N1   N 2  N1
No. of e  in excited state
* In order to achieve pop. Inversion, we must have an energy state which has a long life
time. Such an energy state is called Metastable state (life time > 10 -8 sec).
Main components:
1. Active medium : medium in which pop. Inversion occurs
2. Energy source
3. Optical resonator: consists two mirrors facing each other. It encloses active
medium one is fully reflective, one is partially reflective.
Its function is to s intensity of laser beam
Ruby Laser
3 Level – solid state : Laser giving a pulsed laser beam of  = 6943 Ao .
Xe - flash tube of  = 5500 Ao
Population inversion is between
Metastable state E2 and G.S
E1Optical pumping is used with Xe.
Flash tube of  = 5500Ao Ruby rod
itself acts as resonating cavity
/resonator. If the length of the ruby
n
rod L  if acts like resonant
2
cavity intensity becomes max. high intensity laser beam escapes from partially silvered
end.

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Drawback  pulsed radiation Heat generates

He – Ne Laser
It is a 4 – level gas LASER giving a continuous laser beam of   6328 Ao
Population inversion is between the 5s and 3p states of Neon. He atom are used to help us
achieve population inversion in Ne atoms by inelastic atomic collisions. He atoms are
excited by powerfull electric discharge . If the length between the two mirrors L  n  2
resonance condition is satisfied , high intensity beam is obtained.

When N 2  N1  Laser transition but if N 2  N1  No Laser transition

 Again have to give pumping (gap) will come pulsed radiation
E2 is always empty (∵ 10 – 6 sec life time)
E3  E3 Laser transition ∴ Always E3 have greater e  than G.S He – Ne LASERs are
tunable Lasers. 4 level lasers are more efficient than 3 – level laser . Solid state lasers
gives high intensity radiation than gas because of density of atom is more for solids.Co2
LASER : Here Co2 : N2 : He are taken in the ratio of about 21 : 3: 5 .N2 molecules are
useful to achieve POP inversion in Co2 molecules Population inversion occurs in Co2
molecules beween Asymmetric stretching mode and stretchable SB mode symmetric
bending Co2 laser gives two outputs 10.6 m and 9.6 m in IR – [Link] is useful in
increasing the efficiency of the laser by evacuating Co2 molecules from lower state. It is
an industrial laser IR region   Co2 laser used in industries for welding cutting … etc.
Spatial and Temporal Coherency
L
C
T
L – is called coherence length
T – is called coherence time
C - velocity of light

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Molecular spectra (fluted spectra)

They are band spectra . All Mol. Spectra are observed in Absorption. The Total Energy of
a diatomic molecule can arise in 3 modes
1. Electronic Energy (Ee)
2. Vibration Energy (Ev)
3. Rotational Energy (Er)
Ee  Ev  Er
If the mol. Is in the [Link] of Ee, Ev and undergoes transitions only between rotational
states we get pure Rotational spectra which lies in FIR and Microwave [Link]
energies are about 10 2 eV (0.01 eV)  If the mol. Is in the [Link] of Ee and undergoes
transitions between different Ev, Er states we get Vibrational Rotational spectrum which
lies in IR – region (IR – spectra) Photon energies are about 1ev  0.1ev .If the molecule
undergoes transitions in all Ee, Ev, Er states we get Electronic spectrum – lies in visible
and UV regions. Photon energies are > 1.7 eV
Pure Rotational Spectrum (Rotating dipole concept
This is mostly observed in absorption. Homonuclear mole, like H2 , O2 , ….[Link]
polyatomic mole like Co2 , CH4 etc. will not have permanent electric dipole moments
They are called Non Polar [Link] mol. Like co, Hcl, H2 o , ….etc. have
permanent electric dipole moment and called polar [Link] polar molecules give
pure rotational [Link] Energy of a diatomic [Link]
L2
EJ  As L  J ( J  1) J = 0,1,2 ….. Rotational quantum no.
2I
2 mm
EJ  J ( J  1) Here I   r 2 r – bond length   1 2 In wave no. of terms
2I m1  m2
2 h2
F ( J )  EJ / hc  J  J  1 cm1 (or) F ( J )  BJ ( J  1) cm1 B cm 1
2 Ihc 8 2 Ic
called Rotational constant
 The wave [Link] are 0,2B,6B,12B,20B ….

Selection rules in pure rotational spectra J  1

F ( J  1)  B ( J  1)( J  2)  BJ ( J  1)  B ( J  1)  J  2  J  F  J  1  2B  J  1 cm1
 The wave no. terms of the spectral terms are
J  0  2B 
 2 B i.e F (0  i)  F (0)  2 B(0  1)  2 B
J  1  4B 

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J  2  6 B 2 B i.e F 1  i   F (i )  2 B (1  i )  1B
J  4  8B
J  5  10B
 The wave no. different between any two successive lines in the pure rotational
spectrum of rigid diatomic mol. Is 2B cm – 1 .For higher J values molecule becomes non –
rigid rotor. Here centrifugal distortion effects the rotational states.
Here F ( J )  BJ ( J  1)  DJ 2 ( J  1)2 D  B is called centrifugal distortion constant
F ( J  1)  F ( J )  B( J  1)( J  2)  D( J  1)2 ( J  2)2  BJ ( J  1)  DJ 2 ( J  1) 2
 B( J  1)  J  2  J   D( J  1) 2  J  2   J 2   2B( J  1)  ( J  1)2 ( J  1)
2
 
1
 2B( J  1)  4D( J  1) cm At higher rotational levels (high temp) mol. Becomes non-
3

rigid. Wave no. different  ses with increasing ‘J’ . Isotope Effect:. For heavier isotope
11   , I '  I and B '  B
Rotational Vibrational Spectrum
It is also given by polar molecules only it is also observed as absorption [Link]
vibration Energy of a LHO is Ev  (v  1 2 )hv v  0,1, 2,..... called vibrational [Link]. In
Ev v  v
wave no. terms G (v)    v  1 2  cm 1 G(v)  v0  v  1 2  cm1  v0  
hc c  c
G(v ')  G(v)  v0 (v  3 2  v  1 2) G (v)  g (v)  vo cm 1 Only one band should occur at
vo cm1 but the observed spectrum contains overtones also at about 2vo ,3vo etc.
Occurrence of overtones implies that molecule is behave like anharmonic oscillator (not
harmonic). This anharmonicity is of two types
1. Occurrence of overtimes implies that possible this is because the P.E curve is not
strictly  parabola
i.e. Total Energy E  f ( x 2 )  g ( x3 ) g  1
This is called Mechanical Anharmonicity
2. Overstones occurring at lesser and lesser than 2v0 ,3v0 ....(1.9v, 2.8v...)
Implies that the dipole moment is not varying linearly with x – distance . This is called
Electrical Anharmonicity.
The two peaks in [Link] are due to isotope effect.
For heavier isotope  '   , f '  f
1 K
Frequency f  
2
 V  1
J   1
Selection rules
At room temp. 99% of the molecules exist in V = 0 ground state.
v  1 implies transitions from v  0 to v  1 . In every vibrational state different
rotational levels exist. The selection rules in vib- rot. Spectrum are V  1 J  1

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If
V  1 V  1
 we get P – branch lines  we get R - branch lines
J  1  J  1 
For a vib- Rot transition we have : F (v)  G(v)  BJ ( J  1)  vo (v  1 2)
vF ,G   F (v ')  G (v ')    F (v)  G (v)   B( J  1)( J  2)  vo (v  3 2)  BJ ( J  1)  vo (v  1 2)

vF ,G  2 B( J  1)  vo cm1 For a harmonic oscillator V ( x)  F ( x 2 )

For anharemonic oscillator V ( x)  F ( x 2 )  g ( x3 ) Solving [Link] equation for this
V ( x) gives wave no. term G (v)  ve (v  1 2)  ve xe  v  1 2  cm 1
2

 x 
ve  hypothetical frequency for which when v  1 2 , E = 0 v0  ve 1  e  cm 1
 2
v vx
Here the Ground state term for G (o)  e  e e cm1 V = o  Ground state
2 4
v  x 
G (o)  e 1  e  cm 1 For V = 0 to V = 1 , wave no. difference
2 2
3 3 1 vx
v  G (v1 )  G (v)  ve  ve xe  ve  e e v  ve (1  2 xe ) cm1
2 4 2 4
For v = 0 to v= 2 transition  v  2ve1  3 xe  cm 1
Occurrence of overstones implies v  1, 2..... possible . This is because the dipole
moment is not varying with internuclear distance (electrical anharmonicity).Overtones
occurring at lesser and lesser than 2vo ,3vo etc. is because P.E. curve is not strictly a
parabola (mechanical anharmonicity)Vibration terms are around 1000 – 3000 cm – 1 wave no. of
rot terms are round 1 – 10 cm – 1 For diatomic mol. It is about 10 cm – 1 .Triatomic mol. It is
1 cm – 1 . Vibrational – Rot Energy: According Born – oppenhermer rotation and
vibration of a mol. Are independent of each other
Etotal  Evib  Erot . F ( J )  G(v)  BJ ( J  1)  DJ 2 ( J  1) 2  ve (v  1 2)  ve xe  v  1 2 
2

vJ ,v  vo  2mB m  1, 2.... etc. For J  1  vJ ,v  vo  2mB (R-branch)

J  1  vJ ,v  vo  2mB ( P – branch).The wave no. different between any ‘2’
successive lines in either [Link] (or) R- branch lines is 2B cm – 1 But successive lines in
p-branch get farther and In R-branch they get [Link] is called Break down of Born
oppenhemer approximation i.e vibration affect each other (which is opposite to the Born
happens assumption)

Degree of Freedom
For each molecule 3 – coordinates are required hence 3 of. For N – atoms we have 3N –
dof’s . In 3 N – 3 . Here for linear molecules 2 – Rot dof’s . For non-linear molecules 3
rot dof’  for vibration only 3N – 5  for linear 3N – 6  for Non – linear For N –
atoms in a mole there are N – 1 bond  N – 1 streching modes are possible  No. of

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bending modes is 3N  5  N  1  2 N  4  For linear 3 N  6   N  1  2 N  5 

for non linear e.g for Co2  3 atom Total dof = 3N = 3(3) = 9

Total d of = 3N = 3 (3) = 9 3 are trans  for rotation and vibration

d of = 6
Co2  linear  2 – rotations  for vibration only 4  (3N – 5)
Out of 4  2 are bond stretching operation  for bending  2  (2N-4) e.g. For H2
o molecule: 3 N  3(3)  9  total . 3 N  3  9  3  6  vibration and rotation
Rotation  non linear  rotation  3
Bond stretching  N-1  2 Sym. stretching
asymmetric

O
H H O
H H
Bending  1  (bend angles change )
In short Atom  3 d

Scattering
Scattering is of two types:
1. If the wavelength changes after scattering it is incoherent scattering
e.g. Compton effect (1922 – in x –rays)
2. Raman effect (1928 optical Analog of compton effect)
If the  - doesnot change after scattering coherent scattering e.g. Rayleigh scattering
(appearance of blue light in sky) I  v4 ( I  1  ) Blueness of sky , Reddishness of rising/
setting sun are all due to the coherence scattering called Rayleigh scattering where
Intensity of scattered light I  v 4 or I  1  4

Raman Effect
When an intense beam of monochr light is scattered from an Organic solution like C6 H 6
toluene , Ethyl alchol etc. a scattered radiation contains new lines symmetricallydisplaced
about the parent line (Rayleigh line).New line are called Roman [Link] wavelength
components are stokes [Link] wavelength components are Antistokes [Link]
lines are more intense than Antistokes lines  I St  I A.S  .All Roman lines are strongly
polarized .Thus Roamn effect is an incoherent scattering phenomenon and is called
Optical Analog of Compton effect.

Fluorescence Raman Effect

1. Only longer wavelength comes 1. Both longer and shorter
2. Freq. depends on scatterer 2. Fre. Shifts depends on scatterer
3. Lights are unpolarised 3. Lines are strongly polarized

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Raman effect can be explained only by Quantum Mech/Theory

 E  E2 
E1  hv1  E2  hv2 V2  v1   1 
 h 
1. E1  E2 then v2  v1 , 2  1 (parent line)
2. E1  E2 then v2  v1 , 2  1  ( Antistokes lines)
3. E1  E2 then v2  v1 , 2  1  stokes lines
Raman effect is mainly due to polarization () of the [Link] is Anisotropic
(Anisotropy means of any property of mol. Changes withdirection then that is called
Anisotropy). Induced dipole moment is proportional to E
Or
  
  E When an oscillating E is applied  E  Eo sin 2 ft  EMR frequency
   Eo sin 2 ft This oscillation dipole can absorb / exist. This frequency radiation
only - Ray leights coherent scattering. If the molecule has some internal motion like
vibration or rotation it gets superimposed on this oscillation. Let fv be the vibration
frequency  changes as  o   sin 2 fvt   -  o   sin 2 f v t  Eo sin 2 ft
 Eo
  o Eo sin 2 ft  cos 2  f  fv  t  cos 2  f  fv  t  i.e The oscillating dipole
2 
has two additional frequency f  f v and f  f v superimposed on f .

Vibratinal Raman spectra (Effect)

Raman  vo   G (v  1)  G (v )   vo  
vViber .
vraman
vibration
 vraman
vibration
 vo  

Rotaional Raman spectra

Selection rules for rotational Raman spectra J  0, 2 J  2 is because in each
rotation
rotation polarization changes 2 times VRaman  vo   F ( J  2)  F ( J ) 
 vo   B ( J  2)( J  3)  BJ ( J  1)   vo   B( J 2  5 J  6)  B( J 2  J ) 
rotation
vRaman  vo   B  4 J  6  vraman
Rotaion
 2 B(2 J  3) or 4B  J  3 2  or  B(4 J  6)

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Vraman
vibration
 
Vraman
rotation
  B(4 J  6)

Raman spectrum can be used for homonuclear mole. Like H 2, N2, O2 an dsymmeteric
polyatomic molecules like Co2 , CH4 …. Also (to find their properties – Raman spectra
only used). The separation between the two successive stoke lines or Antistoke lines is
4B cm – 1 . The separation between 1 st Antistoke and 1st stoke line is 12 B cm – 1 .There
are 4 types of molecules depending on symmetry
Rotation of molecule :
For a molecule I a , I b , I c are principle moments of inertia
1. Linear 2. Symmetric 3. Sphereical 4. Asymmetric
1. Linear molecules:
Here I a  0, Ib  I c e.g. HCN, Co2 , C2H2 , OCS (oxycarbon sulphide)

Ib
Ib
Ic Ic
16 18 16 M  14
M 2 M 6
000 H C  N
com Ia Ia

2. Symmetric tops
e.g. : CH3Cl, CH3F, NH3 , BF3 , BCl3
If I a  I b  I c that is called prolate
molecules If I a  I b  I c that is oblate

3. Spherical tops: most symmetric

CH 4 , CCl4 , SF6 Here I a  I b  I c
4. Asymmetric tops: most asymmetric
e.g. CH3OH, CH2 CHCl, H2O Here I a  I b  I c
Most of the molecules are of this type. If the
vibration or rotation of the molecule doesn’t
change its polarizability  = 0 only fundament
frequency [Link] order to be Raman active a
moles rotation or vibration must cause some
change (either in magnitude/in direction). Of [Link] IR and MW activity
the mole motion must produce a change in the dipole moment of the molecule.
H 2O, H 2 S , SO2 best molecules (Asymmetric tops) CHCl3 (chloroform) , CH3Cl
and NH3 - symmetric top molecules

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CH4, CCl4 , SF6, SIH4 – spherical top molecules..For linear mol. Having centre of
symmetry (diatomic mole) H2, O2 , Co2 etc..The effects of nuclear spin will be
observed in Raman (as well as) .But for O2 and Co2 Nuclear spin I  0 , every alternate. J
level is absent. For H2 mol. I  0 , lines have alternating [Link] symmetric top,
molecule pure rotation about top has no (top).Change in polarizability. Hence they are
Roman Inactive For sph. Top mole also  doesnot change they are also completerly
Roman Inactive. Normally all rotations of Asymmetric top molecules are Raman active

Vibration Raman spectra

In vibration Raman spectra if the mole has little or no symmetry all vibrational modes are
Raman active. For Co2 S – S is Raman Active, where As and SB modes are Raman
Inactive.
Rule of Mutual Exclusion
If a mol. Has centre of symmetry then Raman active vibration are IR – Inactive and vice
versaIf there is no centre of symmetry then some vibrations may be both Raman and IR
activee.g. CO2 Molecule – has centre of symmetry.
Raman IR
Sym. Stretching, v1 active inactive  s.s & v1 = 1320 cm – 1
[Link] v2 inactive active  A.S v2 = 2349 cm – 1
Bending v3 inactive active  B.M v3 = 667 cm – 1

H 2 N 2 F2 CS2 , CH 4 are Raman active

 
SS SS

H 2O, NO2 , SO2 show both IR and Raman active (not having CDS.)
Either they are bend or linear but not symmetric

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