CHEM 352: Examples for chapter 3.

1. a) Show that sp
2
hybrid orbital h =
1

3
_
s +

2p
x
_
is normalized. The
functions s and p
x
denote normalized hydrogenlike atomic orbitals.
b) Normalize the following molecular orbital =
s,A
+
s,B
where
s,A
and
s,B
are normalized and is a parameter. Use the notation S for overlap
integral to simplify the result.
Solution:
a)
_
|h|
2
d =
1
3
_ _
s +

2p
x
_
2
d =
1
3
_

_
_
s
2
d
. .
=1
+

2
_
sp
x
d
. .
=0
+2
_
p
2
x
d
. .
=1
_

_
=
1
3
3 = 1.
b) N
2
_
||
2
d = N
2
_
|
s,A
+
s,B
|
2
d
= N
2
_

_
_
|
s,A
|
2
d
. .
=1
+2
_

s,A

s,B
d
. .
=S
+
2
_
|
s,B
|
2
d
. .
=1
_

_
= N
2
(1 + 2S +
2
) = 1 N =
1

1+2S+
2
2. Consider hydrogen molecule (H(A)H(B)) with the LCAO-MO orbitals
formed from the atomic orbitals 1s
A
and 1s
B
:
1
g
= N
1
(1s
A
+ 1s
B
) and 1

u
= N
2
(1s
A
1s
B
)
a) Show that the Slater determinant corresponding to the ground state
solution is antisymmetric.
b) One of the excited states of H
2
corresponds to the following Slater
determinant:

MO
=
1

1
g
(1)(1) 1

u
(1)(1)
1
g
(2)(2) 1

u
(2)(2)

What electron conguration does this correspond to?

1
Solution:
a) The Slater determinant is:

MO
=
1

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

=
1

2
[1
g
(1)1
g
(2)(1)(2) 1
g
(1)1
g
(2)(1)(2)]
=
1

2
1
g
(1)1
g
(2)
. .
symmetric
[(1)(2) (2)(1)]
. .
antisymmetric
A product of symmetric and antisymmetric functions given overall an anti-
symmetric function.
b) This corresponds to an electron conguration (1
1
g
)
1
(1

u
)
1
with parallel
spins. The term symbol is therefore
3
.
3. Determine the valence electron congurations and bond orders in the fol-
lowing molecules: C
+
2
, C
2
, C

2
, N
+
2
, N
2
, N

2
, O
+
2
, O
2
, O

2
. Which of these
molecules are paramagnetic and what are their term symbols?
Solution:
Use the correlation diagram to determine the order of orbitals for C
2
:
C
+
2
...2
2
g
2
2
u
1
3
u
Bond order = 1.5 (weakest bonding);
2

u
.
C
2
...2
2
g
2
2
u
1
4
u
Bond order = 2;
1

+
g
.
C

2
...2
2
g
2
2
u
1
4
u
3
1
g
Bond order = 2.5 (strongest bonding);
2

+
g
.
N
+
2
...2
2
g
2
2
u
1
4
u
3
1
g
Bond order = 2.5;
2

+
g
.
N
2
...2
2
g
2
2
u
1
4
u
3
2
g
Bond order = 3.0 (strongest bonding);
1

+
g
.
N

2
...2
2
g
2
2
u
1
4
u
3
2
g
1
1
g
Bond order = 2.5;
2

g
.
O
+
2
...2
2
g
2
2
u
3
2
g
1
4
u
1
1
g
Bond order = 2.5 (strongest bonding);
2

g
.
O
2
...2
2
g
2
2
u
3
2
g
1
4
u
1
2
g
Bond order = 2;
3

g
.
O

2
...2
2
g
2
2
u
3
2
g
1
4
u
1
3
g
Bond order = 1.5 (weakest bonding);
2

g
.
4. Sketch the molecular orbital diagram for B
2
molecule by using 1s, 2s and
2p atomic orbitals and all 10 electrons. What is the term symbol?
Solution:
The MO diagram is:
2
The term symbol is
3

g
.
5. a) Sketch a molecular orbital diagram for XeF molecule and determine the
electronic conguration. Would XeF
+
have shorter bond length than XeF?
b) Construct a molecular orbital diagram for the double bond (4 electrons)
in ethene by using the carbon sp
2
hybrid orbitals as basis set. Choose the
energy order of the and orbitals in such a way that a stable molecule is
formed.
c) Explain why Ne
2
molecule is not stable. Why are atoms with the out-
most s and p orbitals full (e.g. the octet electronic conguration) chemically
inert?
Solution:
a) XeF is not a homonuclear diatomic molecule. Thus the atomic orbitals
that form MOs originate from dierent principal quantum number levels.
The MO diagram is:
3
The bond order for XeF is (87)/2 = 0.5 and for XeF
+
(86)/2 = 1. Thus
the equilibrium bond length for XeF
+
is expected to be shorter than for XeF.
b) Consider the MOs of the C=C fragment:
Note that the order of the and

orbitals must be as shown above. If this

was not the case, the C=C fragment would not be bound!
c) All the resulting bonding and antibonding orbitals become fully occupied.
As antibonding orbitals cause more repulsion than bonding orbitals binding,
the result is no chemical binding. In general, the octet electronic structure
in atoms (e.g. rare gases) tends to lead to ecient population of the anti-
bonding molecular orbitals and hence they are chemically inert.
4
6. Use the variational principle to obtain the lowest energy solution to the
hydrogen atom Schrodinger equation in spherical coordinates by using the
following trial wavefunctions:
a)
trial
= e
kr
with k as a variational parameter.
b)
trial
= e
kr
2
with k as a variational parameter.
Note that both trial functions depend only on r and the angular terms dis-
appear from the Laplacian. You may nd the following integrals useful:
_

0
x
n
e
ax
dx =
n!
a
n+1
_

0
x
m
e
ax
2
dx =
[(m+1)/2]
2a
(m+1)/2
[n + 1] = n!, with 0! = 1 (n is integer)
[n + 1] = n[n]

_
1
2

Solution:
Use the variational principle and employ spherical coordinates in integrations:
E =
R

trial
H
trial
d
R

trial

trial
d
a)
_

trial

trial
d =
_

0
e
2kr
4r
2
dr
. .
d
= 4
_

0
r
2
e
2kr
dr =

k
3
_

trial
H
trial
d =
_
_
e
kr
_
_

h
2
2m
e

e
2
4
0
r
_
_
e
kr
_
d
=
_

0
_
e
kr
_
_

h
2
2m
e
_

2
r
2
+
2
r

r
_

e
2
4
0
r
_
_
e
kr
_ _
4r
2
dr
_
=
4 h
2
2m
e
_

0
_
e
kr
_
_
k
2
e
kr

2k
r
e
kr
_
r
2
dr
e
2

0
_

0
e
2kr
r
r
2
dr
=
4 h
2
2m
e
_

0
e
2kr
(r
2
k
2
2kr)dr
e
2

0
_

0
re
2kr
dr
5
=
2 h
2
k
2
m
e
_

0
r
2
e
2kr
dr
. .
=
2
(2k)
3
+
4 h
2
k
m
e
_

0
re
2kr
dr
. .
=
1
(2k)
2

e
2

0
_

0
re
2kr
dr
. .
=
1
(2k)
2
=
h
2
2m
e
k
+
h
2
m
e
k

e
2
4k
2

0
These results give:
_

Hd
_

d
=
_

h
2
2m
e
k
+
h
2
m
e
k

e
2
4k
2

0
_
/
_
/k
3
_
=
h
2
k
2
2m
e
+
h
2
k
2
m
e

e
2
k
4
0
=
h
2
k
2
2m
e

e
2
k
4
0
This expression must be minimized with respect to variational parameter k:
dE
dk
= d
_
h
2
k
2
2m
e

e
2
k
4
0
_
/dk =
h
2
k
m
e

e
2
4
0
= 0
k =
m
e
e
2
4
0
h
2
E =
1
2
m
e
e
4
(4
0
)
2
h
2
= hcR
where R is the Rydberg constant.
b) The logic is exactly the same as in part a).
_

trial

trial
d =
_

0
e
2kr
2
4r
2
dr
. .
d
=
4[3/2]
2(2k)
3/2
=

3/2
(2k)
3/2
The Laplacian of this function is given by:

trial
=

r
_
2kre
kr
2
_
+
2
r
(2kr) e
kr
2
=
_
4k
2
r
2
6k
_
e
kr
2
6
Thus the energy expectation value is (without normalization):
_

o
_

2 h
2
k
2
r
2
m
e
+
3k h
2
m
e

e
2
4
0
1
r
_
e
2kr
2
4r
2
dr
= 4
_

0
_

2 h
2
k
2
r
4
m
e
+
3k h
2
r
2
m
e

e
2
r
4
0
_
e
2kr
2
dr
=
8 h
2
k
2
m
e
_

0
r
4
e
2kr
2
dr
. .
[5/2]
2(2k)
5/2
=
3

8(2k)
5/2
+
12k h
2
m
e
_

o
r
2
e
2kr
2
dr
. .
[3/2]
2(2k)
3/2
=

4(2k)
3/2

e
2

0
_

0
re
2kr
2
dr
. .
[1]
2(2k)
=1/(4k)
=
3
3/2
h
2
4m
e

2k
+
3
3/2
h
2
2m
e

2k

e
2
4
0
k

trial

trial
d
_

trial

trial
d
=

3
3/2
h
2
4me

2k
+
3
3/2
h
2
2me

2k

e
2
4
0
k

3/2
(2k)
3/2
=
3 h
2
k
2m
e
+
6 h
2
k
2m
e

e
2

2k
2
3/2

0
=
3 h
2
k
2m
e

e
2

2
3/2

0
To nd the minimum value for energy (with respect to k), we calculate the
rst derivative and set it to zero:
E =
3 h
2
k
2m
e

e
2

2
3/2

E
k
=
3 h
2
2m
e

e
2
2

2
3/2

k
= 0
k =
_
m
e
e
2
3

2
3/2

0
h
2
_
2
=
m
2
e
e
4
18
3

2
0
h
4
The total energy at this point is:
7
E =
3 h
2
2m
e

m
2
e
e
4
18
3

2
0
h
4

e
2

2
3/2

m
e
e
2
3

2
3/2

0
h
2
=
m
e
e
4
12
3

2
0
h
2

2m
e
e
4
12
3

2
0
h
2
=
m
e
e
4
12
3

2
0
h
2
=
8
3
hcR 0.85hcR
c) The function in a) gives lower energy and therefore that trial function is
better.
7. Calculate the orbitals of allyl radical (corresponding to localized struc-
ture
.
CH
2
C=CH
2
, however, assume delocalization in your calculation) by
using the H uckel theory.
a) What is the wavelength of the LUMO HOMO electronic transition
when = 22, 000 cm
1
?
b) Calculate the charge densities and bond orders from the H uckel wavefunc-
tion. Denitions for these observables are given below:
Electron density on atom i:
(i) =
N
MO

j=1
|c
j
i
|
2
n
j
where n
j
is the number of electrons on orbital j and c
j
i
is the H uckel MO
coecient of the basis function centered on atom i for orbital j. The sum-
mation runs over the occupied orbitals.
Bond order between atoms i and j:
bond order =
N
MO

k=1
c
k
i
c
k
j
n
k
8
where the symbols are dened as above.
Solution:
First we construct the secular equation (matrix form) corresponding to the
H uckel approximation:
_
_
E 0
E
0 E
_
_
_
_
c
1
c
2
c
3
_
_
= 0
Denote x = ( E)/ and recall this set of equations has a non-trivial
solution only if the corresponding determinant is zero:

x 1 0
1 x 1
0 1 x

= 0
By expanding this determinant, we get:
x(x
2
1) x = x
3
2x = x(x
2
2) = 0 x =
_
_
_
0
+

2
E =
_
_
_

2
+

2
Thus we have the following energetics for the orbitals:
a) The energy dierence between HOMO and LUMO orbitals is:
E = E
LUMO
E
HOMO
=

2 =

2 =

2 (22, 000cm
1
)
9
E = 3.86eV (320 nm)
b) Next we calculate the coecients c
1
, c
2
and c
3
for the lowest energy orbital:
Here E = (

2), which with (E)c

1
+c
2
= 0 gives c
2
=

2c
1
. Ex-
actly the same way, equation c
2
+(E)c
3
= 0 gives c
2
=

2c
3
. Finally,
normalization gives: c
2
1
+ c
2
2
+ c
2
3
= 1 c
2
1
+ (

2c
1
)
2
+ c
2
1
= 4c
2
1
c
1
=
1
2
and by considering c
3
the same way, we also get c
3
=
1
2
.
Thus we have:
E = +

2 with c
1
=
1
2
, c
2
=
1

2
, c
3
=
1
2
E =

2 with c
1
=
1
2
, c
2
=
1

2
, c
3
=
1
2
For E = , we have: c
1
=
1

2
, c
2
= 0, c
3
=
1

2
.
The electron density on atom 1 can be obtained by squaring the atomic basis
function coecients and weighing this by the number of electrons on that
orbital:
Atom 1 (i = 1):

3
j=1
|c
j
i
|
2
n
j
=
_
1
2
_
2
2 +
_
1

2
_
2
1 +
_
1
2
_
2
0 = 1.
Atom 2 (i = 2):

3
j=1
|c
j
i
|
2
n
j
=
_
1

2
_
2
2 + 0
2
1 +
_

2
_
2
0 = 1.
Atom 3 (i = 3):

3
j=1
|c
j
i
|
2
n
j
=
_
1
2
_
2
2 +
_

2
_
2
1 +
_
1
2
_
2
0 = 1.
The total charge (three electrons) is distributed evely to all three atoms
and therefore the partial charges on carbon atoms are equal.
The bond orders can be valuated as follows:
Bond between atoms 1 and 2 (i = 1 and j = 2):
N
MO

k=1
c
k
i
c
k
j
n
k
=
_
1
2
__
1

2
_
2 +
_
1

2
_
0 1 +
_
1
2
__

2
_
0 =
1

2
10
Bond between atoms 2 and 3 (i = 2 and j = 3):
N
MO

k=1
c
k
i
c
k
j
n
k
=
_
1

2
__
1
2
_
2 +0
_

2
_
1 +
_

2
__
1
2
_
0 =
1

2
The bond order is less than one ( 0.707), which indicates that the bond is
not very strong.
11