Group Theory-Part 12 Correlation Diagrams

Correlation Diagrams
C734b 2008
Correlation Diagrams C734b 2008
Spin Postulate
An electron possesses an intrinsic angular momentum in addition to its normal orbital angular momentum L S
r Electrons exhibit a magnetic moment
where
r B r e = ge S = ge S h 2me r
where me mass of the electron and B Bohr magneton
B =
eh = 0.9274 10 23 JT 1 2me
s = for electrons and ge =2.00232
S is an angular momentum like L with components Sx, Sy and Sz and associated self-adjoint operators:
,S ,S ,S 2 S x y z
which obey similar commutation relationships as
,L ,L ,L 2 L x y z
,S ,S S x y z
all commute with
2 S
but not with each other
Only one component, say
S z
can have a common set of eigenfunctions with
2 S
,S ,S ,S 2 S Note: x y z
2 L , L , L , L f(x, y, z) which means they commute with x y z
r r r Total angular momentum of electrons J = L + S

commutation relationships as
where
,J 2 J i
obey similar
,L 2 L i
3
For any angular momentum
r A
as
+,A Can define raising and lowering operators A

+ =A + iA A x y =A iA A x y
Let the eigenfunctions of
2 and A be ja , m a A z respectively.
with eigenvalues ja ( ja + 1)h 2 and m a h
ma
ranges from ja to +ja in integer steps.
Can show that:
j , m = h j ( j + 1) m (m 1) j , m 1 A a a a a a a a a
Correlation Diagrams C734b 2008 4
r 1 Since s = 2
for electrons s 2 = s(s + 1)h 2 =
3 2 1 h and m s = m s h = h 4 2
The two spin eigenvectors are: s, m s = and s, m s =

1 1 ,- (spin down) 2 2
1 1 , (spin up) 2 2
1 1 1 1 , , =1 2 2 2 2
and
1 1 1 1 ,m , =0 2 2 2 2
Spin functions are orthonormal: normalized and orthogonal.
Spherical Symmetry for many electron atoms (N)
Hamiltonian is given by:
=H +H +H rr H o ee LS
kinetic energy of electrons and the e- - nucleus interactions H o
If
=H H o
alone (1,2, L , N ) = (1)(2 )L (N )
with each one e- state characterized by 4 quantum numbers, n, , m, ms
H ee
electron electron interaction which couples angular momenta of the individual electrons in 2 possible ways
Low Z elements (Z ~< 40)

r r L = li
i
r r S = si
i
Spin-orbit interactions couples
r r r r v L and S to form J = L + S
Russell-Saunders coupling
High Z elements (Z > 40)

Orbital and spin angular momenta of each electron couples first:
r r These then couple to total J = ji
i
r r r ji = li + si total angular momenta of each individual electron.

j-j coupling Note: can have intermediate coupling for intermediate Z although L-S (Russell-Saunders) scheme is often used as a first approximation.
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Note:
>H rr For low Z H ee L.S
r v <H r r Q L S ~ 2 Z2 For high Z H ee LS

2 fine-structure constant =7.29735 x 10-3 ~1/137 Coupled energy states in Russell-Saunders coupling are called multiplets and these are described by spectral terms of the form 2S+1L
L= 0
S P D F G L
spin multiplicity 2S+1
4 L
How to get L or S?
Given any angular momenta
r A = A1 + A 2 , A1 + A 2 1, L A1 A 2
r r A1 and A 2
m a = A,A + 1, L ,+ A
If there are > 2 angular momenta, couple A1 and A2 A12, then A12 + A A123, etc. The effect of spin-orbit interactions is to split the multiplets into their components with term symbols: 2S+1LJ
1 r r = E (L, S)[J(J + 1) L(L + 1) S(S + 1)] Spin-orbit splitting: LS 2

where
(L, S ) spin-orbit coupling constant > 0 for < -filed shells

smallest J lies lowest in energy
If < 0 for > -filled shells largest J lies lowest in energy Hunds third rule Example: (ns)1(np)1 configuration 1 = 0; 2 = 1 s1 = ; s2 =
L=1 S = 1, 0
terms are 3P, 1P
When S = 0, L = 1, J = 1
1P
1 3P 2,1,0
When S = 1, L = 1, J = 2,1,0
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P2
P1
- -2
P0
-Hee has 2 parts: a Coulomb repulsion J and an exchange interaction K which is non-classical and is a consequence of the Pauli-Exclusion Principle which requires the total wave function to be antisymmetric with respect to the interchange of two spin particles (electrons which are fermions).
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(ns) (np)
1
1
P1
+K J
3
-K
P2
3 3
P1
P0
Ho
Hee
HL.S
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Intermediate Crystal Fields (low Z elements)

Let HCF term in the Hamiltonian which describes the electrostatic interaction with the surrounding ions or ligands.
if if if
>H H CF ee
strong crystal field
>H >H r r intermediate crystal field H ee CF LS

<H r r weak crystal field H CF LS
-Consider an atomic term with angular momentum L. A representation, DL, for any group of proper rotations can be found using angular momentum eigenfunctions: spherical harmonics {YLM} as a 2L+1 degenerate basis set. Note: here DL instead of L is used for historical reasons.
Can show:
( )Y M (, ) = Y M R 1{, } R L L
M L iM
= Y (, ) = e
Y (, )
M L
This means each member is transformed into itself multiplied by a numerical coefficient e-iM
e iL 0 D L ( ) = M 0
0 e i (L 1) M 0
L 0 L 0 O M iL L e
(D L ( )) = e
iL
e
p =0
2L
= e iL
(e (
i 2L +1)
1 e i 1
e e
i 2 i 2
a geometric progression
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(2 L + 1) sin 2 (DL ( )) = sin 2

Can calculate the character system for any group of rotations for any L, and if reducible, can do this in the usual way into a direct sum of IRs
Note: for (E)
As 0 lim
0
sin
[(2L + 1)]
2 sin 2 = lim
0
(2L + 1) = 2L + 1
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16
Table shows (DL) for = /2, 2/3, and and the splitting of the free ion states in Oh symmetry for L 2 Splittings in lower symmetries deduced from correlation tables, or by finding direct sums using common classes in both groups.
Parity
If inversion, i, is a group operation then the wave function will have definite parity. Parity eigenvalue of the inversion operator.
= = i
If If
= + i = i
even or gerade g-parity odd or ungerade u-parity
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The parity of
Ylm (, ) = ( 1)
s 0
parity = + 1 1 + 1 1
For several electrons:
l=
p 1
d 2
f 3
(1,2,3,K , N ) = (1) (2)L (N )
l li parity = ( 1) i = ( 1) i i
This means the parity is determined by the electron configuration, NOT on the total orbital angular momentum, L.
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Example:
nsnp nd2
parity = ( 1)
0 +1
= 1 all terms are u states = +1 all terms are g states = +1 all terms are g states
parity = ( 1)
2+ 2
npnp
parity = ( 1)
1+1
+ + Now, if i G and the parity is even DL (iIR) = DL ( IR)
If the parity is odd DL (iIR) = DL ( IR)
] [
Character table will have the form given by the following example for Oh
O h = O Ci
Oh g u
{O} i{O} (O ) (O ) (O ) (O )
Therefore, need only consider {O} and work out parities later.
19
Example: a) Into what states does the Russell-Saunders term d2:3F split in Oh symmetry? b) What is the effect of a D3 trigonal distortion? a) 3F L = 3, S = 1. Since S is unaffected by electrostatic fields (only by magnetic fields), triplet terms in the free ion remain triplets in Oh symmetry Parity = (-1)2+2 = +1 g terms. From table given for DL L = 3: states are 3A2g, 3T1g, 3T2g b) Select classes that are common to both groups and reduce the IR from the group of higher symmetry in the group of lower symmetry
20
From character tables:
O A2 T1 T2
E 8C3 1 1 3 0 3 0
6C '2 1 1 1
D3 A1 A2 E
E 2C3 1 1 1 1 2 1
3C '2 1 1 0
actual character table
Find from reduction:
O A2 T1 T2
D3 A2 A2 E A1 E
This is the way correlation tables are derived. Procedure can be used if such tables are not available.
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Strong Crystal Fields

-one where electrostatic interactions due to ion surrounding > electron-electron interactions in ion.
Consider the effect on free ion electron configurations and deduce states and their degeneracies
Later: will correlate strong to intermediate CFs. In Oh symmetry 5d orbitals t2g (dxy, dyz, dxz) + eg (dz2, dx2-y2) and E(t2g) < E(eg) since these orbitals point at the ligands. Opposite scenario occurs in Td symmetry where E(eg) < E(t2g)
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To determine states in a strong field, use Bethes method of Descending Symmetry Method based on: (i) Electrostatic fields dont affect spin (ii) If (1,2) = i(1)j(2) and i(1) forms a basis for i and j(2) forms a basis for j means i(1)j(2) forms a basis for the direct product i j Due to Pauli Exclusion Principle: (1) 2 electrons in the same orbital generates a singlet state only. (2) 2 electrons in different orbitals generates a singlet and a triplet state.
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Example: Find all states that forma d2 configuration in a strong field of Oh symmetry. Correlate with those of the free ion and those of an ion in an intermediate field. Configurations are (t2g)2, (t2g)1(eg)1 and (eg)2 Parity of d2 terms g. Simply use O character table to reduce direct products O character table:
O A1 A2 E T1 T2
E 8C3 1 1 2 3 3 1 1 1 0 0
3C 2 1 1 2 1 1
6C 4 1 1 0 1 1
6C '2 1 1 0 1 1
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Consider (eg)2 6 states: 2 singlets when the 2 electrons in the same eg orbital, and 1 singlet and 1 triplet when they are in different eg orbitals 6 state functions are contained in the direct product of e g e g
e g e g reduces in O to a1 a 2 e
Dont know which are singlets and triplets. Bethess method is to lower the symmetry until all representations in the direct product are one-dimensional Examine the Correlation Tables In D4h symmetry: A1g A1g; A2g B1g; Eg A1g + B1g
e1g a1g + b1g orbitals; that is, they split.

2 2 a 1g 1 A1g eg 1 1 3 a1 1g b1g B1g , B1g 2 b1g 1 A1g
Since the electrostatic field does not affect spin means that the 3B1g state in D4h must have come from 3A2g state in Oh. All other states must be singlets.
in Oh d2 1A1g, 3A2g, 1Eg Total degeneracy = 6 as expected ( = (2S+1)x state degeneracy = 1x1 + 3x1 +1x2)
Next: do t2g2 configuration in Oh Reduce in C2h
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t 2g t 2g = a1g e g t1g t 2g
ag
ag bg
ag bg bg
ag ag bg
t 2g t 2g (O h ) (a g a g b g ) (a g a g b g ) (C 2h )
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Put in 2 electrons:
2 ag (1)1 A g 1 1 3 a1 g (1)a g (2) A g , A g 1 1 3 a1 g (1)b g B g , B g 1 1 3 a1 g (2)b g B g , Bg 2 ag (2)1 A g 2 bg 1 A g
3 3 3 We are looking for triplet state(s) in C2h that transform as A g Bg Bg
In Oh this must be the T1g state Therefore, states are: 1 A1g 1 E g 3 T1g 1 T2g Total degeneracy = 1x1 + 1x2 + 3x3 + 1x3 = 15
in O h
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Lastly: t2g1eg1. Method of descending symmetry is not necessary since both singlets and triplets are allowed (t2g, eg are different orbitals)
t 2g e g t1g t 2g in O h
Therefore, states are:
1
T1g ,3T1g ,1T2 g ,3T2 g
Total degeneracy = 1x3 + 3x3 + 1x3 + 3x3 = 24
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31
Correlation Diagrams
Connects strong field states to intermediate field states
Rules: 1.) Non-crossing rule: states of same symmetry and spin multiplicity may not cross. 2.) Hunds rules: a) states of highest spin multiplicity lie lowest in energy b) terms with the same S, the one with highest orbital L lies lowest. Rules apply strictly only to ground states.
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Next: consider an nd8 configuration Need to observe 2 new principles. 1.) doubly occupied orbitals contribute A1g to direct products and 0 to S and MS due to the Pauli Exclusion Principle. 2.) Account for spin-pairing energy. Electrons in degenerate levels tend to have unpaired spins whenever possible. It is an empirical fact that spin-pairing in eg orbitals requires more energy than in the t2g orbitals
d8 :
2 5 3 4 4 E t6 2g e g < E t 2g e g < E t 2g e g
) (
) (
Q# e g pairs are :
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2 E eg < E (e g t 2g ) < E t 2 2g
( )
( )
Therefore d8 behaves as if, relative to d2, ordering of the t2g and eg levels have been inverted. Means, the correlation diagram for d8 is like that for d2 but with the ordering of the high-field states inverted. Can show: d10-n (Oh) like dn (Td) and dn (Oh) like d10-n (Td)
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Correlation Diagrams

Correlation Diagrams C734b 2008

r Electrons exhibit a magnetic moment

s = for electrons and ge =2.00232

Correlation Diagrams C734b 2008

which obey similar commutation relationships as

all commute with

but not with each other

Only one component, say

can have a common set of eigenfunctions with

2 L , L , L , L f(x, y, z) which means they commute with x y z

r r r Total angular momentum of electrons J = L + S

Correlation Diagrams C734b 2008

For any angular momentum

+,A Can define raising and lowering operators A

with eigenvalues ja ( ja + 1)h 2 and m a h

ranges from ja to +ja in integer steps.

Can show that:

for electrons s 2 = s(s + 1)h 2 =

The two spin eigenvectors are: s, m s = and s, m s =

Spin functions are orthonormal: normalized and orthogonal.

Correlation Diagrams C734b 2008

Spherical Symmetry for many electron atoms (N)

Hamiltonian is given by:

kinetic energy of electrons and the e- - nucleus interactions H o

alone (1,2, L , N ) = (1)(2 )L (N )

with each one e- state characterized by 4 quantum numbers, n, , m, ms

Correlation Diagrams C734b 2008

Low Z elements (Z ~< 40)

Spin-orbit interactions couples

High Z elements (Z > 40)

r r r ji = li + si total angular momenta of each individual electron.

Correlation Diagrams C734b 2008

>H rr For low Z H ee L.S

r v <H r r Q L S ~ 2 Z2 For high Z H ee LS

Correlation Diagrams C734b 2008

Correlation Diagrams C734b 2008

1 r r = E (L, S)[J(J + 1) L(L + 1) S(S + 1)] Spin-orbit splitting: LS 2

(L, S ) spin-orbit coupling constant > 0 for < -filed shells

terms are 3P, 1P

Correlation Diagrams C734b 2008

Correlation Diagrams C734b 2008

Correlation Diagrams C734b 2008

Intermediate Crystal Fields (low Z elements)

strong crystal field

>H >H r r intermediate crystal field H ee CF LS

Correlation Diagrams C734b 2008

(2 L + 1) sin 2 (DL ( )) = sin 2

Note: for (E)

Correlation Diagrams C734b 2008

Correlation Diagrams C734b 2008

even or gerade g-parity odd or ungerade u-parity

Correlation Diagrams C734b 2008

(1,2,3,K , N ) = (1) (2)L (N )

Correlation Diagrams C734b 2008

+ + Now, if i G and the parity is even DL (iIR) = DL ( IR)

If the parity is odd DL (iIR) = DL ( IR)

Correlation Diagrams C734b 2008

Correlation Diagrams C734b 2008