5.

04, Principles of Inorganic Chemistry II

MIT Department of Chemistry
Lecture 28: Atomic State Wavefunctions and Energies

Atomic wave functions for states (or terms) may be determined by the
application of raising and lowering operators… for electronic wave functions

( ) [(
L ±
mi msi =
 i ± mi + 1  i  mi )( )]
(m
2
i ± 1, msi )
1�
 3  1 2�
( )
S±
mi msi =

± msi 
 msi 
mi , msi ± 1
 2  2 
( )�
… the same operator may be applied to multi e- functions, Y
,m

+

Beginning with the highest order term
(4, 4, 0, 0) =
(2 2) . May
determine
(4, 3, 0, 0) by application of L_ to

1
L
 (4, 4, 0, 0) =
[(4
4 + 1)(4 + 4)] 2  (4,3, 0, 0) =
2 2 (4,3, 0, 0)

+
1 +
1 +

L
 (2,2) =
[(2
2 + 1)(2 + 2)] 2  (1,2) +
[(2
2 + 1)(2 + 2)] 2  (2,1)
 +
+

= 2
 (1,2) +  (2,1)
 
recall that these are Slater
i.e.

1  +
 (1)



(2)



(2)
+ 
(1)
determinants

 1 2 1 2 
2 �
+

+
1 1 (1) 1 (2) 1 2 (2) 1 (1)
= =

2  (1)  (2) 2  (2)  (1)
+

+

2 1 2 2

1 
+ +


1 (2)2 (1)
2 (1)2 (2)

2
+

+
(1,2) =
(2,1) 

+

(2,1)

1  +

+ 
so overall (4,3, 0, 0) = (2,1)
(2,1)
2 

5.04, Principles of Inorganic Chemistry II Lecture 28

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functions for the configuration d2
Table removed due to copyright considerations.

5.04, Principles of Inorganic Chemistry II Lecture 28 �

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Now need to determine the energies of these terms

…. for a d2 configuration, 1S, 3P, 1D, 3F and 1G eigenvalues appear only along
the diagonal. Need only to calculate the energy of one of these terms (since
eigenvalues within a block are the same). For the d2 example being worked
in these notes, the following diagonal elements will be determined,

E 1 G =  (4, 4, 0, 0)   (4, 4, 0, 0)�

( )

E( F ) =  (3,3,1,1)�  (3,3,1,1)�
3

E( D) =  (2,2, 0, 0)�  (2,2, 0, 0)

1

The perturbation operator H’ is composed of 1e- (μi) and 2e- (Qij) operators

N N N
 = μ̂ + 12� Q̂
i ij�
i=1 i=1 j=1�
i
j�

Ze2 e2�
where μ̂i =
+ eV(ri ) and Q̂ij =
ri r�
ij

one-electron integrals:

Ze2
μ(ab) = a μ̂i b = a
+ eV(ri ) b
ri
= I(na ,
a ;nb ,
b ) 
a ,
b m
a ,m
msa ,ms
b b

where I(na ,
a ;nb ,
b ) =  R na ,
a (r) μˆ i R nb ,
b (r) r2dr
0

from above expression, only integrals composed of wavefunctions possessing

the same n and
quantum numbers will be non-zero.

5.04, Principles of Inorganic Chemistry II Lecture 28

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two-electron integrals:
e2
Q(a b c d) = ab Q̂ij cd = ab cd
rij

=  c (

k=0�
k
a ,m
a ) (
;
c ,m
c ck
d ,m
;
b ,m

d
)
b�

a constant! R k (abcd) (msa ,msc ) (msb ,msd ) (m
a +m
c ,m
b +m
d )
1
 4
2
2

k
(
where c
a ,mm
;
b ,mm

a b
) =

 2k +1 
 
0 0
Y
a ,m
(,)Yk,m

a a
•m
b (,)Y

b ,m
b (,) sindd

exchange terms under the integral must preserve the antisymmetrizer

m
b
m
a
ck (
a ,m
a ;
b ,m
b ) = (
1) ck (
b ,m
b ;
a ,m
a )

The Rk (abcd) integrals historically are expressed as F or G integrals in

standardized tables

k


r< 2 2
R k (abcd) = e2   R na
a (ra )R nb
b (rb ) k+1
R nc
c (rc )R nd
d (rd )ra rb dra drb
0 0
r>
where

R k (na ,
a ;nb ,
b ;na ,
a ;nb ,
b ) = F k (na ,
a ;nb ,
b ) same n and

R k (na ,
a ;nb ,
b ;nb ,
b ;na ,
a ;\) = Gk (na ,
a ;nb ,
b ) different n and

F parameters are typically simplified in tables per the following relations:

F0 = F 0
1 2
F2 = F
49�
1� 4
F4 = F
441

and expressed in Racah parameters as

A = F0 – 49F4�
B = F2 – 5F4�
C = 35F4�

From these integrals, may now determine the energies of the states derived
from the d2 configuration. The solution of these integrals are provided in
standardized tables. Owing to time constraints… the summary of the solution
is shown on the next page.

5.04, Principles of Inorganic Chemistry II Lecture 28

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Summarizing the term energies for a d2 ion (Kh symmetry)

1�
S F0 + 14F2 + 126F4 (A + 14B + 7C)�
1�
G F0 + 4F2 + F4 (A + 4B + 2C)

3 2
2 P F0 + 7F2 - 84F4 (A + 7B) for a given d ion, the energies
(nd)
2I (nd;nd) of the observed states are used
to determine F0, F2 and F4

1�
D F0 - 3F2 + 36F4 (A - 3B + 2C)�

3�
F F0 - 8F2 - 9F4 (A - 8B)

For a given d2 ion, the energies of the observed states are used to determine
F0, F2, and F4.

For instance:

V3+ (d2) term
Eexp / cm-1

1�
S not observed
1�
G 18,400 F0 = 11,2000 cm 1
3�
P 13,000  F2 = 1,590 cm-1
1�
D 10,600 F4 = 115 cm 1
3�
F 0

5.04, Principles of Inorganic Chemistry II Lecture 28 �

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