Lecture 18 Title : Fine Structure : multi-electron atoms

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In this lecture we will concentrate on the fine structure of the multielectron atoms.

As discussed in the previous lecture that the fine structure arises due to spin orbit coupling.

Here we will discuss about the spin orbit coupling in case of more than one electron and their
effect on terms transitions.
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The Hamiltonian for the multielectron atoms

H = H * + H1 + H Spin Orbit
J
2 N 2 N
where H * = i + U ( ri )
2me i 1 =i 1
=

N
Z e2 N
e2
where i =
U ( ri ) =

i 1 ri
+
i < j rij

e2
N N
e2
H1
and= Non-Spherical part only
i < j rij i < j rij

H Spin Orbit = ASO li . si L

The Spin-orbit interaction couples the total spin and total S

orbital angular momentum (L) to form the total angular
momentum J.

The figure-18.1 represents the vector diagram and l1 s2

accordingly we write l2
s1
J= L + S (for one electron atoms).

Figure 18.1
Because of this coupling, the one electron wavefunctions
e2
L ml S ms which are the eigenfunctions of H CentralField +
rij e2
+ + AL.S
i, j

are no more the eigenfunctions of the total Hamiltonian H. H =H CF

i , j rij

l1ml 1 s1ms 1 LmL JmJ

l1ml 2 s2 ms 2 Sms
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The eigenfunctions of the H will be J mJ which are the coupled wavefunctions and can be
derived from the uncoupled wavefunctions L ml S ms , as described in previous lectures.

According to the coupling of angular momentum the value of J = J =

L + S ,......... L S and the
2 S +1
notation is LJ where L = 0,1, 2,3,.....are S , P, D, F respectively.

So the perturbation energy

ESO =J mJ ASO L.S J mJ

Now, J= L + S

J 2 = L2 + S 2 + 2 L.S
1 2 2
L.=S J L S 2
2

And thus, the energy correction due to the spin-orbit interaction is

ASO
=
ESO J mJ ASO L.S =J mJ [ J ( J + 1) L( L + 1) S (S + 1)] (18.1)
2
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2S + 1 is the known as multiplicity. Indicates the degeneracy of the level due to spin.

If S = 0 => multiplicity is 1: singlet term.

If S = 1/2 => multiplicity is 2: doublet term.

If S = 1 => multiplicity is 3: triplet term and so on.

In the following we will discuss the effect of spin-orbit interaction on terms to terms transitions.

Singlet levels

S =0 ; J =L+S =L
ASO
=
ESO J ( J + 1) L (=
L + 1) 0
2

1 1
P P1

1 1
S S0

Selection Rules : l = 1, L = 0, 1, S = 0, J = 0, 1
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Doublet levels

Transition from 2 D to 2 P

For 2 D=L 2,=S 1 =, J 5 ,3

2 2 2

Using equation-18.1

5 5
2
ESO=

ASO
D5
2 2 2 2 ( )
+ 1 2 ( 2 + 1) 1 =
2
1 + 1 A
2 (
SO )
A
2 2 2 2 ( ) 2 2 (
ESO 2 D3 = SO 3 3 + 1 2 ( 2 + 1) 1 1 + 1 =

3
2

ASO )
For 2 P =L 1,=S 1 ,=J 3 ,1
2 2 2

3 3
ESO
= 2 ASO
P3
2 2 2 2 ( )
+ 1 1(1 + 1) 1 =
2 2 (

1 + 1 ASO
2 )
A
2 2 2 2
( ) 2 2 (
ESO 2 P1 = SO 1 1 + 1 1(1 + 1) 1 1 + 1 =


ASO )
So the construction of energy levels

2
D5

ASO
2

3
2
D
ASO 2
2 D3
0 2
1 2 3
2
P3

ASO 2

2
2
P
ASO
2
P1
2
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It is important to know the degeneracy lifted by this spin-orbit interaction. The degeneracy for
1
2
D level is 10 (2 L + 1)(2 S + 1)= (2.2 + 1)(2. + 1)= 10
2

When this level splits into 2 D5 and 2 D3 , then

2 2

2
D5 the degeneracy is 6 because =
J 5 , m= 5 , 3 , 1 , 1 , 3 , 5 . All mJ levels will
2 2 J 2 2 2 2 2 2
be degenerate. The mJ degeneracy will not be lifted until the external magnetic field is applied.

Similarly, 2 D3 the degeneracy is 4 because =

J 3 , m= 3 , 1 , 1 , 3 .
2 2 J 2 2 2 2

1
The degeneracy for 2 P level is 6 (2 L + 1)(2 S + 1)= (2.1 + 1)(2. + 1)= 6
2

When this level splits into 2 P3 and 2 P1

2 2

2
P3 the degeneracy is 4 because =
J 3 , m= 3 , 1 , 1 , 3 . All mJ levels will be
2 2 J 2 2 2 2
degenerate. The mJ degeneracy will not be lifted until the external magnetic field is applied.

Similarly, 2 P1 the degeneracy is 2 because= = 1 , 1 .

J 1 ,m
2 2 J 2 2

We will discuss the later the effect of magnetic field on these levels.

Transitions : as shown in the adjacent figure-18.2

ASO

For transition 1 1 = 0 + ASO
2 0

3
For transition 2 2 =
0 + ASO
ASO
2 3 1 2

3 Figure 18.2
For transition 3 3 =
0 ASO
ASO
2 2

> ASO
In general ASO so transition pattern will be 2 > 1 > 3 .
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3
D 3P transition

S =1 J = 3, 2, 1
For 3D term So,
L=2 3
D3 , 3 D2 , 3 D1

S =1 J = 2, 1, 0
For 3P term
L =1 3
p2 , 3 p1 , 3 p0

Now, let us calculate the perturbation energies for these levels using equation-18.1. We take the
spin-orbit constants A2 and A1 for 3D and 3P respectively.

ESO ( 3 D=
3)
A2
2
[12 6 =
2] 2 A2 , ESO ( 3 D2 ) =
A2
2
6 6 2 =
A2

ESO ( 3 D1 ) =
A2
2
2 6 2 = 3A2

ESO ( 3 P2=) A1
2
[6 2 =
2] A1 , ESO ( 3 P1 ) =
A1
2
2 2 2 = A1

ESO ( 3 P1 ) =A21 [0 2 2] =2 A1

Transition energies are 3

D3

1 = 0 + 2A2 A1 3
D2
3
D
2 = 0 A2 A1
3
D1
0
1 2 3 4
5
3 = 0 A2 + A1 6
3
P2
4 = 0 3A2 A1
3 3
P P1
5 = 0 3A2 + A1
3
6 = 0 3 A2 + 2 A1 P0
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The Observed transition of Calcium is given in this figure below.

1
4
2
3

Figure-18.3

Observed Observed Observed Calculated

transitions transitions transitions transitions
(nm) (cm-1) (cm-1)

1 = 0 + 2A2 A1 445.47 22448.20 22447.46

2 = 0 A2 A1 445.59 22442.16 22442.16

3 = 0 A2 + A1 443.50 22547.91 22547.91

4 = 0 3A2 A1 445.66 22438.63 22438.63

5 = 0 3A2 + A1 443.57 22544.36 22544.38

6 = 0 3 A2 + 2 A1 442.54 22596.68 22597.26

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From transitions 2 and 3

E0 A2 A1 =
22442.16
E0 A2 + A1 =
22547.91

= 2 A1 22547.9 22442.26
= 105.7
A1 = 52.875 cm 1

From transitions 2 and 4

E0 3 A2 A1 =
22438.63
E0 A2 A1 =
22442.16

= 2 A2 22442.16 22438.63
3.53
A2 = = 1.765 cm 1
2

And 0 = 22496.8 cm 1

The other transitions calculated from these values are given in the table.
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Let us take another example, the transitions of Copper [3d94s4p] 4F [3d94s5s] 4D

J = 7 ,5 ,3 , 1
4 S=3 2 2 2 2
For D term 2 So, 4
L=2 D7 , 4 D5 , 4 D3 , 4 D 1
2 2 2 2

J = 9 ,7 ,5 , 3
4 S=3 2 2 2 2
For F term 2
4
L=3 F9 , 4 F7 , 4 F5 , 4 F3
2 2 2 2

For 4 F
9 A 9 11 3 5 9
E ( J = ) = 1 . 3.4 . = A1
2 2 2 2 2 2 2

7 A 63 63
E ( J = ) = 2 [ ] =0
2 2 4

5 A 35 63 A 28 7
E ( J = ) = 1 [ ] = 1 . = A1
2 2 4 2 4 2

3 A 15 63 A 48
E ( J = ) = 1 [ ] = 1 . = 6 A1
2 2 4 2 4

For 4 D

7 A 63 39 A 24
E ( J = ) = 2 [ ] = 2 . = 3 A2
2 2 4 2 4

5 A 35 39 A 4 A
E ( J = ) = 2 [ ]= 2 . = 2
2 2 4 2 4 2

3 A 15 39 A 24
E ( J = ) = 2 [ ] = 2 . = 3 A2
2 2 4 2 4

3 A 3 39 A 36 9
E ( J = ) = 2 [ ] = 2 . = A2
2 2 4 2 4 2
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The constructed energy level diagram is shown in this figure below.

4
F9
2
4
F 4
F7
2
4
F5
2

4
F3
2

4
D7
2
4
D
4
D5
2
4
D3
2

4
D1
2

Selection rules: derived from Wigner-Eckart theorem discussed earlier

l =1, S =0, J =0, 1 . The J = 0 J = 0 is forbidden.

The transition energies are

9
(1) v (4 F9 4 D7 ) = o 3 A2 + A1
2 2 2

o 3 A2
(2) v (4 F7 4 D7 ) =
2 2

A2
o +
(3) v (4 F7 4 D5 ) =
2 2 2

7
o
(4) v (4 F5 4 D7 ) = A1 3 A2
2 2 2
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7 A
o
(5) v (4 F5 4 D5 ) = A1 + 2
2 2 2 2

7
o
(6) v (4 F5 4 D3 ) = A1 + 3 A2
2 2 2

A2
(7) v (4 F3 4 D5 ) = o 6 A1 +
2 2 2

(8) v (4 F3 4 D3 ) = o 6 A1 + 3 A2
2 2

9
(9) v (4 F3 4 D1 ) = o 6 A1 + A2
2 2 2

The experimental set up for recording the copper 4 F 4 D spectrum.

Cu electrodes

High voltage
Fiber optic coupled
Cu arc power supply
spectrometer

The copper 4 F 4 D spectrum.

80000
Copper (4F -> 4D)
465.23
Intensity (arb. units)

60000 453.28 460.86

474.03

40000
458.9
470.57
451.07
20000

0
450 460 470 480 490 500
Wavelength (nm)
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Assigning the observed three transitions as follows.

Transitions Observed wavelength (nm) Observed transition energy

(cm-1)

4 F7 4 D5 458.90 21791.2
2 2

4 F9 4 D7 465.23 21494.7
2 2

4 F3 4 D 1 470.57 21250.8
2 2

So we have three equations below to solve for obtaining three parameters.

9
o 3 A2 + A1 =
21494.7
2
o 3 A2 =
21250.8
A2
o + =
21791.2
2

From these above equations, we get

A2
o + =21791.2
2
o 3 A2 =21250.8
7
A2 = 540.4
2
540.4 X 2
=A2 = 154.4 cm 1
7
o = 21250.8 + 3*154.4 = 21714
9
A1 = 21494.7 21250.8 = 243.9
2
243.9* 2
=A1 = 54.2 cm 1
9
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Transitions Transition Calculated Calculated observed

energy transition transitions (nm) transitions (nm)
-1
energy (cm )
4
F9 4 D7 o 3 A2 +
9
A1
21494.7 465.23 465.23
2 2
2
4
F7 4 D7 o 3 A2 21250.8 470.57 470.57
2 2

4
F7 4 D5 o +
A2 21791.2 458.90 458.90
2 2
2
4
F5 4 D7 7
o A1 3 A2
21061.1 474.8 474.03
2 2
2
4
F5 4 D5 7
o A1 +
A2 21601.5 462.93 460.86
2 2
2 2
4
F5 4 D3 7 21987.5 454.80 453.28
2 2 o A1 + 3 A2
2
4
F3 4 D5 o 6 A1 +
A2 21464.8 465.88 -----
2 2
2
4
F3 4 D3 o 6 A1 + 3 A2 21850.8 457.65 ------
2 2

4
F3 4 D1 o 6 A1 +
9
A2
22082.4 452.84 451.07
2 2
2
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Summary of Atomic Energy levels

Gross structure of the atomic energy levels:

It covers largest interactions within the atom:

(a) Kinetic energy of electrons in their orbits.

(b) Attractive electrostatic potential between positive nucleus and negative electrons

(c) Repulsive electrostatic interaction between electrons in a multi-electron atom.

These interactions give energies in the 1-10 eV range and upwards. It determine the
spectrum range whether a photon is IR, visible, UV or X-ray.

Fine structure:

Spectral lines often come as multiplets. E.g., H line.

This smaller interactions within atom, called spin-orbit interaction.

The origin of this interaction is

Electrons in orbit about nucleus give rise to magnetic moment which interacts with spin of the
electrons. This introduces splitting of the energy levels and produces small shift in energy.

Hunds rule :

(1) Of the terms given by equivalent electrons, those with greatest multiplicity lie deepest,
and of these the lowest is that with the greatest L

(2) Multiplets formed equivalent electrons are regular when less than half the shell is
occupied, but inverted when more than half shell is occupied.
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Recap

In this lecture we have seen the effect of spin orbit coupling on the fine structure of the
multielectron atoms.

We have discussed the transitions between the various spin multiplicity energy levels, sometime
called as multiplets.

We have also gone through the experiments in the copper transitions and also learnt how to
assign the transitions.

We also learnt how to evaluate the spin-orbit constant term for a level from the observed
transitions.