CHEMISTRY 373 - TUTORIAL 11

PRACTICE FOR DIATOMIC MOLECULES AND VARIATION THEORY

MARCH 29

1. In 1971 a paper was published that applied the normalized variation function
Nexp[-br 2 / a o cr / a o ) to the hydrogen atom and stated that the minimization of
the total energy with respect to the parameters b and c yielded an energy 7 %
above the true groundstate energy for infinite nuclear mass. Without doing any
calculations, state why this result must br in error.

answer : b = 0 and c = 1 should give the exact

normalized solutionsolution
=

1
a 3o

exp[-r/a o ]

2. Consider the trial wavefunction

= C A A + C B B
with the energy
*
Hdv
E =
*
dv
Here A and B are real functions
Minimization of E with respect to CA and C B
affords
( A E )C A + ( ES)C B = 0
( ES)C A + ( B E )C B = 0
where : *A H A dv = A ; *BH Bdv = B
A H Bdv = BH Bdv = ; B Bdv = S
This equations in C A and C B only have solutions provided that
the secular equation is zero
A - E - ES
=0
- ES B - E

a. For A = B show that

E =

1 S

with C A = C B =

1
for E +
2

C A = CB =

1
for E 2

answer :
We have
- E - ES
=0
- ES - E

( - E) = ( - ES)

( - E)2 - ( - ES)2 = 0

E =

1 S

We have
( E + )C A + ( E + S)C B = 0
( E + S)C A + ( E + )C B = 0
As well as the normalization condition
2
2
dv = 1 = C A + C B + 2C A C BS
where w assume that A and B both are normalized
From the first two equation we get
( E + )
CB
1
=
= 1 from the normalization CA = C B =
CA
E +S
2
Substitution of E - affords in a similar way CA = C B =

1
2

b. Assuming that :
1
= 1 S + S2 + O(S3 )
1+ S
1
= 1 + S + S2 + O(S3 )
1- S
where O(S3 ) can be neglected for sufficiently small S
+
show that E + =
is lowered less in energy (compared to
1+ S

than E =
is raised. You can assume that and are negative,
1 S
that S is positive and that (S - ) > 0. In most cases = kS where k is between
1.5 and 2
Answer
We have
E + = ( + )(1 S + S2 )
E = )(1 + S + S2 )
Thus
1 = E + = ( S + S2 ) + (1 S + S2 )
2 = E = (S + S2 ) (1 + S + S2 )
2 1 2S 2 > 0 (by assumption)

c. Consider now the case in which A is of lower energy than B so

that B A > 0
Further assume /( A B ) <<< 1; S/( A B ) <<< 1

Answer :
Now assuming that / | | = -1
( A E )( B E ) ( ES)2 = 0
A B ( A + B )E + E 2 2 + ES2 + 2ES = 0

(1 S2 )E 2 + (2S A B )E + ( A B 2 )
We have for the quadratic equation
ax 2 + bx + c the roots
=

-b + D
2a

; =

-b - D
2a

Here
a = 1 S2 ; b = (2S A B ); D = b 2 4ac; c = A B 2
D = (2S - A B )2 4(1 S2 )( A B 2 )
= ( A B )2 + 4( AS)( BS)

D = ( A B )2 + 4( AS)( BS)
= ( A B ) 1 +

4( AS)( BS)
( A B ) 2

Assuming now that

4( AS)( BS)
<< 1
( A B ) 2
and making use of 1 + x = 1 +

1
x for x << 1
2

We have
D = ( A B )[1 +

2( AS)( BS)
]
( A B ) 2

Substituting D into the expresion for E+ affords

2(1- S2 )E + = A + A 2S + ( A B )
[1 +

2( AS)( BS)
]
A

or
E+ = A +

( AS)2
( A B )

We get in a similar way

E- = A +

( BS)2
( B A )

d. Show again that E- is raised more

in energy than E + is lowered
Answer
This is readily seen from the assumption that
A < B
which implies that ( BS)2 > ( AS)2

e. From the E + values obtained in c find CA and C B

CB
( E + )
=
=1
CA
E +S

t
1 - tS

where t = ( - A ) /( A B ) <<< 1
Thus using 1/1- x = 1 + x + x 2

for x <<< 1

CB
t
=
= t (1 + tS + ....) t
C A 1 - tS
From the normliztion condition
2
2
dv = 1 = C A + C B + 2C A C BS or

1 2
C
C
) = 1 + ( B )2 + 2S( B )
CA
CA
CA

Now substituting

CB
=t
CA

1 2
) = 1 + t 2 + 2St
CA

Thus
CA =

1 + t 2 + 2St

1 2
t St 1
2

CB = CA t = t
Thus
+ = A +

( - A )
B
( A B )

We get in the same way

= B

( - B )
A
( A B )

3. Use simple MO theory to predict the bond order,

the number of unpaired electrons, and the groundstate term
for each of the following molecules :
(a)BF;( b)BN;(c)BeS;(d )BO;(e)NO;(f )CF;(g)CP;
( h )NBr;(i)LiO;( j)ClO;( k ) : BrCl

answer : The term symbols are

(a) 1 + ; (b) 3; (c) 1 + ; (d) 2 + ; (e) 2 ;
(f ) 2 ; (g) 2 + ; (h) 3 ; (i) 2 ; (j) 2 ;
( k ) 1 +

4. Construct a simple molecular orbital diagram for ME, where M is a transition metal and E a
main group atom. On the transition metal consider only the 5 d - orbitals which you can split up into
one d two d and two d . On the main group element consider only the p - orbitals which you
can split up into one p and two p . Assume that only orbitals with the same , , or
symmetry interact. Also assume that the interaction is stronger than the interaction.
What would be the configuration for (a)NbO; (b) : RuO and(c) : MoO
Answer :
(a ) : (1 )2 (1)4 ( )4 (2 )1 ; (b)(1 )2 (1)4 ( )4 (2 )4 ;(c)(1 )2 (1)4 ( )4 (2 )2

2
2x

2y

1x 1y
1

5. Construct a simple molecular orbital diagram for M2 , where M is a transition metal.

On the transition metal consider only the 5 d - orbitals which you can split up into
one d two d and two d . Assume that only orbitals with the same , , or
symmetry interact. Also assume that the interaction is stronger than
the interaction which is stronger than the interaction.
What would be the configuration for (a) Zr2 (b); W2 and (c)Re2

Answer : (a) (1 g )2 (1 u )4 (1 g )2 : (b) (1 g )2 (1 u )4 (1 g )2 ; (c)(1 g )2 (1 u )4 (1 g )4

(c)(1 g )2 (1 u )4 (1 g )2 ; (c)(1 g )2 (1 u )4 (1 g )4 (1 g )2

1u
1xg

1yg

1u1

1u2

1g1

1g2

1xu

1g

1yu