CHAPTER

12 The Chemical Bond

LAIDLER . MEISER . SANCTUARY

Physical Chemistry
Electronic Edition

Problems and Solutions

Chapter 12: The Chemical Bond Bond Energies, Shapes of Molecules, and Dipole Moments

Chapter 12
Bond Energies, Shapes of Molecules, and Dipole Moments
12.1. The attractive energy between two univalent ions M+ and A– separated by a distance r is

137.2
− kJ mol−1
r/nm
Suppose that there is also a repulsive energy given by

0.0975
kJ mol−1
(r/nm)6

Plot the attractive and repulsive energies against r, and also plot the resultant energy, all on the same graph. By differentiating the
equation for the resultant energy, calculate the equilibrium interionic distance and the net energy at that distance.
Solution
12.2. The equilibrium internuclear distance in gaseous LiI is 239 pm, and the dipole moment is 2.09 × 10–29 C m. Estimate the percentage
ionic character of the bond.
Solution

12-2
Chapter 12: The Chemical Bond Bond Energies, Shapes of Molecules, and Dipole Moments

12.3. The following are bond dissociation energies:

D(Li 2 ) = 113kJ mol−1

D(H 2 ) = 435 kJ mol−1
D(LiH) = 243kJ mol−1

a. Use Pauling’s relationship (Eq. 12.78) to estimate the electronegativity difference between Li and H.
b. Estimate the percentage ionic character of the Li—H bond, given the following covalent radii:
Li: 126 pm
H: 36 pm

(Note: Since the Pauling relationship leads to dipole moments in debyes, it is often convenient to work problems of this type taking
the electronic charge as 4.8 × 10–10 esu.)
Solution
12.4. Deduce the shapes of the following, on the basis of valence-shell electron-pair repulsion (VSEPR) theory:

BeCl2, SF6, H3O+, NH +4 , PCl6− , AlF63− ,

PO34− , CO2, SO2, NH 32+ , CO32− , NO3−

(See a freshman chemistry text for help.)

Solution
12.5. Calculate the percentage ionic character of the HCl, HBr, HI, and CO bonds from the following data:

HCl HBr HI CO
Internuclear distance/pm 127 141 160 113
–30
Dipole moment/10 Cm 3.60 2.67 1.40 0.33

Solution

12-3
Chapter 12: The Chemical Bond Molecular Orbitals

Molecular Orbitals
12.6. Use Figures 12.26 and 12.28 to construct molecular-orbital diagrams for the following:

B2, CO, BN, BN2–, BO, BF, OF, OF–, OF+

Deduce the bond order and paramagnetism in each case.

Solution
12.7. Sketch the molecular-orbital diagrams for the following:

N2, O2, C2, F2, CN, NO

Which of these species would you expect to become more stable if (a) an electron is added and (b) an electron is removed?
Solution
12.8. The hydrogen atom wave functions 1sA and 1sB are normalized. Prove that the molecular orbitals σ and σ* given in Eqs. 12.29 and
12.30 are mutually orthogonal.
Solution
12.9. The four sp3 hybrid orbitals are given in Eqs. 12.80–12.83. They are constructed from atomic orbitals, s, px, py, and pz, which are
normalized and mutually orthogonal.
a. The orbitals t1, t2, t3, and t4 are normalized. Prove that this is the case for t3.
b. The orbitals t1, t2, t3, and t4 are mutually orthogonal. Prove that this is the case for t2 and t4.
Solution

12-4
Chapter 12: The Chemical Bond Molecular Orbitals

12.10. Eigenfunctions for sp2 hybridization, with maxima at 120° to one another, can be constructed with reference to the following
diagram:

The plane is chosen as the XY plane, and there will be no contribution from the pz orbital. An orbital along the X axis can be
constructed as a linear combination of the s and px orbitals:
ψ1 = as + bpx
where a and b are numbers to be determined. The orbitals s and px are normalized and orthogonal. To obtain the other two orbitals,
the px and py orbitals are resolved along the two directions 120° from the X axis and are combined with the s orbital:

1 3
ψ 2 = a s − bp x + cp y
2 2
1 3
ψ 3 = a s − bp x − cp y
2 2
Make use of the normalization and orthogonality conditions to determine the numbers a, b, and c.
Solution

12-5
Chapter 12: The Chemical Bond Molecular Orbitals

12.11. Use the procedure of Problem 12.10 to construct two normalized and orthogonal wave functions for sp hydridization, at an angle of
180° to one another.
Solution

12.12. Find the expectation values of the L̂2 operator for the three sp2 hybrid orbitals of Eqs. 12.84–12.86. (Hint: L2 = J(J + 1) ˜ 2 .
Calculate L2 for only i = 1 in the set of orbitals.)

Solution
12.13. As explained in Section 12.6, the exact energy ordering of the 2pσg and 2pπu molecular orbitals depends, to some extent, on the
particular molecule examined. Figure 12.26 shows the energy ordering of the molecular orbitals for the case of the nitrogen and
oxygen molecules. Show for the C2 molecule that we can determine the ordering of the 2pσg and 2pπu molecular orbitals simply by
checking whether the molecule is paramagnetic.
Solution
12.14. Using the LCAO MO technique, determine which of the two arrangements, linear (H – H – H)+ or the triangular H3+, is the more
stable state. Hint: Compute the energy of the molecular orbitals in each arrangement.
Solution
12.15. Calculate the coefficients of the occupied orbitals of butadiene with a value of x = –1.6180. The normalization factor is given by
1/ (cn /c1 ) 2 .

Solution
Group Theory
12.16. Give the point groups to which the following belong: (a) an equilateral triangle, (b) an isosceles triangle, and (c) a cylinder.
Solution
12.17. List the symmetry elements for each of the following molecules, and give the point group:

CHCl3, CH2Cl2, naphthalene, chlorobenzene, NO2(bent),

cyclopropane, CO32− , C2H2
Solution

12-6
Chapter 12: The Chemical Bond Molecular Orbitals

12.18. The condition for optical activity, and for a molecule to exist in two enantiomeric forms, is that the molecule has neither a plane of
symmetry nor a center of inversion. Can H2O2 exist in two mirror-image forms?
Solution
*12.19. Deduce the symmetry species of the following vibrations:

Solution

12-7
Chapter 12: The Chemical Bond Essay Questions

12.20. A molecule having a center of symmetry (i) or having an axis of improper rotation (S) cannot have a dipole moment; all other
molecules can. Note, however, that in tables such as Table 12.3 the symmetry operation S is not always included, since it follows
from other operations (for example, as seen in Figure 12.20, S4 is the product C4σh). The following are molecules that have no center
of symmetry but have no dipole moment:
cyclopropane and cyclopentane
In each case, identify the axis of improper rotation, designate the operation, and relate the operation to the appropriate rotations and
reflections. Which of the point groups in Table 12.3 are such that there can be a dipole moment?
Solution
*12.21. The spectroscopic properties of several inorganic complexes can be explained in terms of the energy splitting of the five 3d orbitals
as a result of the electron-electron repulsion between the 3d electrons and those on the approaching ligands. In the case of octahedral
complexes like [Fe(CN)6]3+, it is seen that the set of five 3d orbitals on Fe give rise to three symmetry-adapted orbitals of what is
known as T2g symmetry (dxy, dyz, dxz) and two of what is known as Eg symmetry (d z 2 , d x2 − y 2 ). If the coordinate system for analyzing
the energy levels of this complex is set up such that Fe is at the origin and the six ligands approach along the three Cartesian axes
(from the positive and negative sides of each), explain which set of orbitals will have higher energy.
Solution
Essay Questions
12.22. Give an account of the valence-shell electron-pair repulsion (VSEPR) theory of the shapes of molecules.
12.23. Explain orbital hydridization, with special reference to sp, sp2, and sp3 hydridization.
12.24. Explain the principles underlying the construction of trial wave functions (a) in the valence-bond method and (b) in the molecular-
orbital method.
12.25. Explain the theory underlying the estimation of bond dipole moments from electronegativities.

A considerable number of problems and solutions relating to molecular structure and spectroscopy are to be found in
T. A. Albright and J. K. Burdett, Problems in Molecular Orbital Theory, New York: Oxford University Press, 1992.
G. J. Bullen and D. J. Greenslade, Problems in Molecular Structure, London: Pion, 1983.
C. S. Johnson and L. G. Pedersen, Problems and Solutions in Quantum Chemistry and Physics, New York: Dover, 1986.

12-8
Chapter 12: The Chemical Bond Solutions

Solutions
12.1. The attractive energy between two univalent ions M+ and A– separated by a distance r is

137.2
− kJ mol−1
r/nm
Suppose that there is also a repulsive energy given by

0.0975
6
kJ mol−1
(r/nm)

Plot the attractive and repulsive energies against r, and also plot the resultant energy, all on the same graph. By differentiating the
equation for the resultant energy, calculate the equilibrium interionic distance and the net energy at that distance.
Solution:
Given: attractive energy, repulsive energy, M+ and A– , distance r
Required: equilibrium interionic distance, net energy
The resultant energy is the sum of the attractive and repulsive energies,

137.2 0.0975
E p / kJ mol−1 = − +
r /nm (r /nm)6

To calculate the equilibrium interionic distance and the net energy we differentiate with respect to r.

12-9
Chapter 12: The Chemical Bond Solutions

dE p 137.2 6 × 0.0975
= −
dr r2 r7
dE p
= 0, r = r0
dr
137.2 6 × 0.0975
0= −
r0 2 r0 7
0 = 137.2r05 − 0.585
1/5
⎛ 0.585 ⎞
r0 = ⎜ ⎟
⎝ 137.2 ⎠
r0 = 0.335 706 964 nm
r0 = 335.7 pm

The net energy is therefore,

137.2 0.0975
E p / kJ mol−1 = − +
0.335 706 964 ( 0.335 706 964 )6

E p = −340.5748032 kJ mol −1
E p = −340.6 kJ mol−1

Back to Problem 12.1 Back to Top

12-10
Chapter 12: The Chemical Bond Solutions

12.2. The equilibrium internuclear distance in gaseous LiI is 239 pm, and the dipole moment is 2.09 × 10–29 C m. Estimate the percentage
ionic character of the bond.
Solution:

Given: d = 239 pm, μ = 2.09 × 10 –29 C m

Required: % ionic character

If the bond were completely ionic, the dipole moment would be given by Eq.12. 73,

μ = qd
μionic = (1.602 ×10−19 C )( 239 ×10−12 m )
μionic = 3.828 78 ×10−29 C m

The percent ionic character is obtained from Eq. 12. 74,

μexp
% ionic character = ×100
μionic
2.09 ×10−29 C m
% ionic character = ×100
3.828 78 ×10−29 C m
% ionic character = 54.586 578 5%
% ionic character = 54.6%

Back to Problem 12.2 Back to Top

12-11
Chapter 12: The Chemical Bond Solutions

12.3. The following are bond dissociation energies:

D(Li 2 ) = 113kJ mol−1

D(H 2 ) = 435 kJ mol−1
D(LiH) = 243kJ mol−1

a. Use Pauling’s relationship (Eq. 12.78) to estimate the electronegativity difference between Li and H.
b. Estimate the percentage ionic character of the Li—H bond, given the following covalent radii:

Li: 126 pm
H: 36 pm

(Note: Since the Pauling relationship leads to dipole moments in debyes, it is often convenient to work problems of this type taking
the electronic charge as 4.8 × 10–10 esu.)
Solution:

Given: bond dissociation energies, d Li = 126 pm, d H = 36 pm, q = 4.8 ×10 –10 esu

Required: | χ Li − χ H | , % ionic character

To find the electronegativity difference between Li and H, we use Eq. 12. 78,

( Eionic )
1/2
= K | χA − χB |

For energies in kJ, we use K = 10.

We calculate Eionic from Eq. 12. 77, therefore obtaining | χ Li − χ H | as,

12-12
Chapter 12: The Chemical Bond Solutions

Eionic = D ( AB ) − ⎡⎣ D ( AA ) D ( BB ) ⎤⎦
1/2

(
Eionic = D ( LiH ) − ⎡⎣ D ( Li 2 ) D ( H 2 ) ⎤⎦
1/2 1/2
)
Eionic = ( 243kJ mol −1
− ⎡⎣113kJ mol−1 × 435 kJ mol−1 ⎤⎦ )
1/2 1/2

Eionic = 21.290 730 91kJ mol−1

( 21.290 730 91kJ mol )

1/2
−1

| χ Li − χ H |=
10
| χ Li − χ H |= 0.461 418 8 D
| χ Li − χ H |= 0.461 D

To calculate percent ionic character we use the procedure used in the previous question.
If the bond were completely ionic, the dipole moment would be given by Eq.12. 73,
μ = qd
μionic = ( 4.8 ×10 –10 esu ) ( ( 36 + 126 ) ×10−12 m )
μionic = 7.776 ×10−20 esu m
μionic = 7.776 D

The percent ionic character is obtained from Eq. 12. 74,

μexp
% ionic character = ×100
μionic
0.461 418 8 D
% ionic character = ×100
7.776 D
% ionic character = 5.933 883 746 %
%ionic character = 5.93 %

Back to Problem 12.3 Back to Top

12-13
Chapter 12: The Chemical Bond Solutions

12.4. Deduce the shapes of the following, on the basis of valence-shell electron-pair repulsion (VSEPR) theory:

BeCl2, SF6, H3O+, NH +4 , PCl6− , AlF63− ,

PO34− , CO2, SO2, NH 32+ , CO32− , NO3−

(See a freshman chemistry text for help.)

Solution:
Given: compounds above
Required: VSEPR shapes
To solve this problem, begin by counting the number of electrons present. Arrange the electrons around each atom such that they will have
a complete octet. Count the number of lone pairs and then deduce the geometry.
BeCl2 No lone pairs Linear
SF6 No lone pairs Octahedral
H3O+ One lone pair Triangular-pyramid
NH +4 No lone pairs Tetrahedral
PCl6− No lone pairs Octahedral
AlF63− No lone pairs Octahedral
PO34− No lone pairs Tetrahedral
CO2 No lone pairs Linear
SO2 One lone pair Bent
NH 32+ No lone pairs Trigonal Planar
CO32− No lone pairs Trigonal Planar
NO3− No lone pairs Trigonal Planar

Back to Problem 12.4 Back to Top

12-14
Chapter 12: The Chemical Bond Solutions

12.5. Calculate the percentage ionic character of the HCl, HBr, HI, and CO bonds from the following data:

HCl HBr HI CO
Internuclear distance/pm 127 141 160 113
–30
Dipole moment/10 Cm 3.60 2.67 1.40 0.33
Solution:
Given: d, μ
Required: % ionic character
To solve this problem, we use the procedure used in problem 12.2.
For HCl, if the bond were completely ionic, the dipole moment would be given by Eq.12. 73,
μ = qd
μionic = (1.602 ×10−19 C )(127 ×10−12 m )
μionic = 2.034 54 ×10−29 C m

The percent ionic character is obtained from Eq. 12. 74,

μexp
% ionic character = ×100
μionic
3.60 ×10−30 C m
% ionic character = ×100
2.034 54 ×10−29 C m
% ionic character = 17.694 417 41%
%ionic character = 17.7%

12-15
Chapter 12: The Chemical Bond Solutions

Repeating for each compound we get,

Ionic character
HCl = 17.694 417 41%
= 17.7%
HBr = 11.820 330 97 %
= 11.8%
HI = 5.461 922 597 %
= 5.46 %
CO = 1.822 942 561%
= 1.8%
Back to Problem 12.5 Back to Top

12-16
Chapter 12: The Chemical Bond Solutions

12.6. Use Figures 12.26 and 12.28 to construct molecular-orbital diagrams for the following:

B2, CO, BN, BN2–, BO, BF, OF, OF–, OF+

Deduce the bond order and paramagnetism in each case.

Solution:
Given: figures 12.26 and 12.28
Required: MO diagrams, Bond Order, paramagnetism
The MO diagrams are based on figures 12.26 and 12.28.
# electrons Bond #unpaired
Configuration Order electrons
B2 10 (1sσ g ) 2 (1sσ*u ) 2 (2sσ g ) 2 (2sσ*u ) 2 (2pσ g ) 2 1 0
CO 14 (1sσ g ) 2 (1sσ*u ) 2 (2sσ g ) 2 (2sσ*u ) 2 (2pσ g ) 2 (2pπ u ) 4 3 0
BN 12 (1sσ g ) 2 (1sσ*u ) 2 (2sσ g ) 2 (2sσ*u ) 2 (2pσ g ) 2 (2pπ u ) 2 2 2
BN2– 14 (1sσ g ) 2 (1sσ*u ) 2 (2sσ g ) 2 (2sσ*u ) 2 (2pσ g ) 2 (2pπ u ) 4 3 0
BO 13 (1sσ g ) 2 (1sσ*u ) 2 (2sσ g ) 2 (2sσ*u ) 2 (2pσ g ) 2 (2pπ u )3 2.5 1
BF 14 (1sσ g ) 2 (1sσ*u ) 2 (2sσ g ) 2 (2sσ*u ) 2 (2pσ g ) 2 (2pπ u ) 4 3 0
OF 17 (1sσ g ) 2 (1sσ*u ) 2 (2sσ g ) 2 (2sσ*u ) 2 (2pσ g ) 2 (2pπ u ) 4 (2pπ*g )3 1.5 1
OF– 18 (1sσ g ) 2 (1sσ*u ) 2 (2sσ g ) 2 (2sσ*u ) 2 (2pσ g ) 2 (2pπ u ) 4 (2pπ*g ) 4 1 0
OF+ 16 (1sσ g ) 2 (1sσ*u ) 2 (2sσ g ) 2 (2sσ*u ) 2 (2pσ g ) 2 (2pπ u ) 4 (2pπ*g ) 2 2 2

Species with NO unpaired electrons are diamagnetic, the rest are paramagnetic.

Back to Problem 12.6 Back to Top

12-17
Chapter 12: The Chemical Bond Solutions

12.7. Sketch the molecular-orbital diagrams for the following:

N2, O2, C2, F2, CN, NO

Which of these species would you expect to become more stable if (a) an electron is added and (b) an electron is removed?
Solution:
Given: compounds above,
Required: MO diagrams, stability
For N2:
The MO diagram is given by Figure 12.26(a).

The electron configuration for N2 is (1sσ g ) 2 (1sσ*u ) 2 (2sσ g ) 2 (2sσ*u ) 2 (2pσ g ) 2 (2pπ u ) 4 . An added electron goes into the anti-bonding 2pπ*g level
and therefore weakens the bond. If an electron is removed from the (bonding) 2pσ g level also weakens the bond.

For O2:
The MO diagram is given by Figure 12.26(b).

The electron configuration for O2 is (1sσ g ) 2 (1sσ*u ) 2 (2sσ g ) 2 (2sσ*u ) 2 (2pσ g ) 2 (2pπ u ) 4 (2pπ*g ) 2 . An added electron goes into the anti-bonding
2pπ*g level and therefore weakens the bond. If an electron is removed from the 2pπ*g level, the bond is strengthened.

For C2:

The MO diagram is similar to Figure 12.26(a) with two less electrons in the 2pπ u level.

The electron configuration for C2 is (1sσ g ) 2 (1sσ*u ) 2 (2sσ g ) 2 (2sσ*u ) 2 (2pσ g ) 2 (2pπ u ) 2 . An added electron goes into the bonding 2pπ u level and
therefore strengthens the bond. If an electron is removed from the 2pπ u level, the bond is weakened.

For F2:
The MO diagram is similar to Figure 12.26(a) with four extra electrons.

12-18
Chapter 12: The Chemical Bond Solutions

The electron configuration for F2 is (1sσ g ) 2 (1sσ*u ) 2 (2sσ g ) 2 (2sσ*u ) 2 (2pσ g ) 2 (2pπ u ) 4 (2pπ*g ) 4 . An added electron goes into the anti-bonding
2pσ*u level and therefore weakens the bond. If an electron is removed from the 2pπ*g level, the bond is strengthened.

For CN:
The MO diagram is similar to Figure 12.26(a) with one less electron.

The electron configuration for CN is (1sσ g ) 2 (1sσ*u ) 2 (2sσ g ) 2 (2sσ*u ) 2 (2pσ g ) 2 (2pπ u )3 . An added electron goes into the bonding 2pπ u level and
therefore strengthens the bond. If an electron is removed from the 2pπ u level, the bond is weakened.

For NO:
The MO diagram is similar to Figure 12.26(b) with one less electron.

The electron configuration for NO is (1sσ g ) 2 (1sσ*u ) 2 (2sσ g ) 2 (2sσ*u ) 2 (2pσ g ) 2 (2pπ u ) 4 (2pπ*g ) . An added electron goes into the anti-bonding
2pπ*g level and therefore weakens the bond. If an electron is removed from the 2pπ*g level, the bond is strengthened.

Thus, in summary,
a. Addition of an electron will strengthen: C2 and CN and will weaken N2, O2, F2, and NO
b. Removal of an electron will strengthen: O2, F2, and NO and will weaken N2, C2 and CN

Back to Problem 12.7 Back to Top

12-19
Chapter 12: The Chemical Bond Solutions

12.8. The hydrogen atom wave functions 1sA and 1sB are normalized. Prove that the molecular orbitals σ and σ* given in Eqs. 12.29 and
12.30 are mutually orthogonal.
Solution:
Given: hydrogen atom wave functions 1sA and 1sB, Eqs. 12.29 and 12.30
Required: proof
Eqs. 12.29 and 12.30 are given by,

σ = 1s A + 1s B and σ * = 1s A − 1s B

We are therefore required to prove that

∫ σσ * dτ = 0
∫ (1s + 1s )(1s
A B A − 1s B ) dτ = 0

Solving for the LHS we get,

∫ (1s ) − (1s ) dτ
2 2
A B

= ∫ (1s ) dτ − ∫ (1s )
2 2
A B dτ

Since we are given that,

∫ (1s ) ∫ (1s )
2 2
A dτ = 1 and B dτ = 1 ,

The integral becomes zero and the LHS becomes equal to the RHS of the equation.
Note that another approach is to recognize that the integral of the product of the wave functions is a product of even and odd functions
about zero. Since the resultant function is odd, the integral must go to zero.

Back to Problem 12.8 Back to Top

12-20
Chapter 12: The Chemical Bond Solutions

12.9. The four sp3 hybrid orbitals are given in Eqs. 12.80–12.83. They are constructed from atomic orbitals, s, px, py, and pz, which are
normalized and mutually orthogonal.
a. The orbitals t1, t2, t3, and t4 are normalized. Prove that this is the case for t3.
b. The orbitals t1, t2, t3, and t4 are mutually orthogonal. Prove that this is the case for t2 and t4.
Solution:
Given: Eqs. 12.80–12.83
Required: prove t3 is normalized, prove t2 and t4 are mutually orthogonal
Eqs. 12.80–12.83 are given by,

1
t1 = (s + p x + p y + p z )
2
1
t2 = (s + p x – p y – p z )
2
1
t3 = (s – p x + p y – p z )
2
1
t4 = (s – p x – p y + p z )
2
a. To prove that t3 is normalized, we take the integral of,

∫t t 3 3 * dτ = ∫ t32 dτ since t3 is real

1
( s − p x + p y − p z ) dτ
2
∫t dτ = ∫
2
3
4
1
=
4∫
( s2 + p x 2 + p y 2 + p z 2 − 2sp x + 2sp y 2 + ...) dτ
All cross terms are zero, and the remainders are unity. The integral is thus,

12-21
Chapter 12: The Chemical Bond Solutions

1
∫t 3
2
dτ = (1 + 1 + 1 + 1)
4

∫t dτ = 1
2
3

Since the integral is equal to one, t3 is normalized.

b. To prove t2 and t4 are mutually orthogonal, we evaluate

∫ t2t4 * dτ = ∫ t2t4 dτ since the functions are real
1 1
∫t t 2 4 dτ = ∫
2
( s + p x − p y − p z ) ( s − p x − p y + p z ) dτ
2
1
=
4 ∫ ( s 2 − p x 2 + p y 2 − p z 2 + ...) dτ

All cross terms are zero, and the remainders are unity. The integral is thus,

1
∫t t 2 4 dτ = (1 − 1 + 1 − 1)
4

∫t t 2 4 dτ = 0

Back to Problem 12.9 Back to Top

12-22
Chapter 12: The Chemical Bond Solutions

12.10. Eigenfunctions for sp2 hybridization, with maxima at 120° to one another, can be constructed with reference to the following
diagram:

The plane is chosen as the XY plane, and there will be no contribution from the pz orbital. An orbital along the X axis can be
constructed as a linear combination of the s and px orbitals:
ψ1 = as + bpx
where a and b are numbers to be determined. The orbitals s and px are normalized and orthogonal. To obtain the other two orbitals,
the px and py orbitals are resolved along the two directions 120° from the X axis and are combined with the s orbital:

1 3
ψ 2 = a s − bp x + cp y
2 2
1 3
ψ 3 = a s − bp x − cp y
2 2
Make use of the normalization and orthogonality conditions to determine the numbers a, b, and c.
Solution:
Given: ψ1, ψ2, ψ3,

12-23
Chapter 12: The Chemical Bond Solutions

Required: a, b, and c
To solve this problem, we make use of the normalization and orthogonality conditions to obtain several expressions containing a, b, and c.

∫ψ dτ = 1
2
1

∫ ( as + bp ) dτ = 1
2
x

∫ ( a s + 2absp + b p ) dτ = 1
2 2 2 2
x x

a ∫ s dτ + b ∫ p dτ = 1
2 2 2 2
x

a 2 + b2 = 1 (1)

This is simplified since the orbitals s and px are normalized and orthogonal.

Additional expressions are,

12-24
Chapter 12: The Chemical Bond Solutions

∫ψ dτ = 1
2
2

2
⎛ 1 3 ⎞
∫⎜ 2
⎜ as − bp x +
2
cp y ⎟⎟ dτ = 1
⎝ ⎠
⎛ 2 2 b 2 3c 2
2 2
⎞
∫ ⎜⎝ a s + 4 p x + 4 p y + ... ⎟⎠ dτ = 1
b2 3c 2
a 2 ∫ s 2 dτ +
4 ∫ ∫ p dτ = 1
p 2
x dτ + 2
y
4
2 2
b 3c
a2 + + =1 (2)
4 4

∫ψ dτ = 1
2
3

2
⎛ 1 3 ⎞
∫ ⎜⎜ as − 2 bp x − 2 cp y ⎟⎟ dτ = 1
⎝ ⎠
⎛ 2 2 b 2 3c 2
2 2
⎞
∫ ⎜⎝ a s + 4 p x + 4 p y + ... ⎟⎠ dτ = 1
b2 3c 2
a ∫ s dτ + ∫ p x dτ +
2 2 2
∫ p dτ = 1
2
y
4 4
2 2
b 3c
a2 + + =1 (3)
4 4

∫ψ ψ 1 2 dτ = 0
⎛ 1 3 ⎞
∫ ( as + bp x ) ⎜⎜ as − 2
bp x +
2
cp y ⎟⎟dτ = 0
⎝ ⎠
⎛ 2 2 b 2 2
⎞
∫⎝⎜ a s +
2
p x + ... ⎟dτ = 0
⎠
2
b
a 2 ∫ s 2 dτ + ∫ p 2x dτ = 0
2
2
b 12-25
a2 + = 0 (4)
Chapter 12: The Chemical Bond Solutions

From (1) and (4),

b2
1 − b2 + =0
2
b2
=1
2
1
b=
2
1
a2 + =1
2
1
a=
2

Using (3),

b 2 3c 2
a2 + + =1
4 4
1 1 ⎛ 1 ⎞ 3c 2
+ ⎜ ⎟+ =1
2 4⎝2⎠ 4
4 + 1 + 6c 2 = 1
2
c= i
3

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12-26
Chapter 12: The Chemical Bond Solutions

12.11. Use the procedure of Problem 12.10 to construct two normalized and orthogonal wave functions for sp hydridization, at an angle of
180° to one another.
Solution:
Given: Problem 12.10
Required: two normalized and orthogonal wave functions for sp hydridization

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12-27
Chapter 12: The Chemical Bond Solutions

12.12. Find the expectation values of the L̂2 operator for the three sp2 hybrid orbitals of Eqs. 12.84–12.86. (Hint: L2 = J(J + 1) ˜ 2 .
Calculate L2 for only i = 1 in the set of orbitals.)

Solution:

Given: Eqs. 12.84–12.86, L2 = J(J + 1) ˜ 2 , i = 1

Required: expectation values of L̂2

Eqs. 12.84–12.86 are given in the text as,

1 2
ψ1 = ψ 2s + ψ 2p x
3 3
1 1 1
ψ 2 = ψ 2s − ψ 2p x + ψ 2p x
3 6 2
1 1 1
ψ 3 = ψ 2s − ψ 2p x − ψ 2p x
3 6 2

We will use a short-hand notation for the integrals by writing,

∞
L2 = ∫ ψ i Lˆ2ψ i dτ = ψ i Lˆ2 ψ i ; i = 1, 2, 3.
i −∞

Now recalling that Lˆ2 = l ( l + 1) ˜ 2ψ nlm , and the orthonormal property of the orbitals belonging to the same atom, (see Problem 12.9), we
find that

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Chapter 12: The Chemical Bond Solutions

1 2
ψ 1 Lˆ2 ψ 1 = ⎡⎣0 ( 0 + 1) ˜ 2 ⎤⎦ 2s 2s + ⎡⎣1(1 + 1) ˜ 2 ⎤⎦ 2 px 2 px
3 3
4
ψ 1 Lˆ2 ψ 1 = 0 + ˜ 2
3
4
ψ 1 Lˆ2 ψ 1 = ˜ 2
3
1 1
ψ 2 Lˆ2 ψ 2 = 0 + ⎡⎣1(1 + 1) ˜ 2 ⎤⎦ 2 px 2 px + ⎡⎣1(1 + 1) ˜ 2 ⎤⎦ 2 p y 2 p y
6 2
2
ψ 2 Lˆ2 ψ 2 = 0 + ˜ 2 + ˜ 2
3
4
ψ 2 Lˆ2 ψ 2 = ˜ 2
3

1 1
ψ 3 Lˆ2 ψ 3 = 0 + ⎡⎣1(1 + 1) ˜ 2 ⎤⎦ 2 px 2 px + ⎡⎣1(1 + 1) ˜ 2 ⎤⎦ 2 p y 2 p y
6 2
2
ψ 3 Lˆ2 ψ 3 = 0 + ˜ 2 + ˜ 2
3
4
ψ 3 Lˆ2 ψ 3 = ˜ 2
3

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12-29
Chapter 12: The Chemical Bond Solutions

12.13. As explained in Section 12.6, the exact energy ordering of the 2pσg and 2pπu molecular orbitals depends, to some extent, on the
particular molecule examined. Figure 12.26 shows the energy ordering of the molecular orbitals for the case of the nitrogen and
oxygen molecules. Show for the C2 molecule that we can determine the ordering of the 2pσg and 2pπu molecular orbitals simply by
checking whether the molecule is paramagnetic.
Solution:
Given: C2
Required: see above
A paramagnetic molecule is one with unpaired electrons. The C2 molecule has 12 electrons. We can write the electron configuration based
on (a) the energy level ordering of Figure 12.26 a or o (b) the energy level ordering of Figure 12.26 b.

a. (1sσ g ) 2 (1sσ*u ) 2 (2sσ g ) 2 (2sσ*u ) 2 (2pπ u ) 4 . All electrons are paired; the molecule is diamagnetic.
b. (1sσ g ) 2 (1sσ*u ) 2 (2sσ g ) 2 (2sσ*u ) 2 (2pσ g ) 2 (2pπ u ) 2 . The electrons in the 2pπ u orbital are unpaired (according to Hund’s Rule) and therefore,
the molecule will be paramagnetic.

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12-30
Chapter 12: The Chemical Bond Solutions

12.14. Using the LCAO MO technique, determine which of the two arrangements, linear (H – H – H)+ or the triangular H3+, is the more
stable state. Hint: Compute the energy of the molecular orbitals in each arrangement.
Solution:
Given: H3+
Required: determine most stable state
We first determine the energy of the molecular orbital for each geometric arrangement. Then place the electrons in the lowest energy
orbital.
The determinant for the linear arrangement is,

α −E β 0
β α −E β =0
0 β α −E

Where we have assumed that the H11 = H 22 = H 33 = α , H12 = H 23 = β , and H13 = 0 . Dividing through by β and setting (α − E ) / β = x , the
determinant reduces to

x 1 0
1 x 1 =0
0 1 x

Which leads to

x3 − 2 x = 0
( )
x x2 − 2 = 0
x=0 and x=± 2

Then the energy for the linear structure becomes,

Elinear = α + β 2 and Elinear = α − β 2

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Chapter 12: The Chemical Bond Solutions

Repeating for the triangular arrangement, we get,

α −E β β
β α −E β =0
β β α −E

Simplifying as above,

x 1 1
1 x 1 =0
1 1 x
x3 − 3x + 2 = 0
( x − 1)( x − 1)( x + 2 ) = 0
x =1 and x =1 and x = −2
Then the energy for the triangular structure becomes,

Etriangular = α + 2β and Etriangular = α − β and Etriangular = α − β

( )
When two electrons occupy the same energy level, E = 2α + 4 β . This energy is lower than the energy E = 2 α + β 2 because β is a
negative quantity. Therefore, the triangular arrangement is predicted to be lower in energy and therefore more stable.

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Chapter 12: The Chemical Bond Solutions

12.15. Calculate the coefficients of the occupied orbitals of butadiene with a value of x = –1.6180. The normalization factor is given by
1/ (cn /c1 ) 2 .

Solution:

Given: butadiene, x = –1.6180, 1/ (cn /c1 ) 2 .

Required: cn

The cn are obtained as the quotient of cn /c1 , divided by ∑ ( c /c )

n 1
2
. For x = –1.6180, we set up the table,

n cn /c1 ( cn /c1 ) cn
2

1 1.000 1.000 0.3717

2 1.6180 2.6180 0.6015
3 1.6180 2.6180 0.6015
4 1.000 1.000 0.3717
∑ (cn /c1 )2 = 7.235 98 (2.6900)2

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12-33
Chapter 12: The Chemical Bond Solutions

12.16. Give the point groups to which the following belong: (a) an equilateral triangle, (b) an isosceles triangle, and (c) a cylinder.
Solution:
Given: a – c
Required: point groups

Shape Symmetry Elements Point Group

a. Equilateral triangle E , 2C3 , 3C2 , σ h , 3σ v , 2S3 D3h
b. Isosceles triangle E , C2 , 2σ v C2v
c. Cylinder E , C∞ , ∞C2 , ∞σ v , σ h , i D∞h

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12-34
Chapter 12: The Chemical Bond Solutions

12.17. List the symmetry elements for each of the following molecules, and give the point group:

CHCl3, CH2Cl2, naphthalene, chlorobenzene, NO2(bent),

cyclopropane, CO32− , C2H2
Solution:

Given: molecules above

Required: symmetry elements, point groups

Molecule Symmetry Elements Point Group

CHCl3 E , C3 , 3σ v C3v
CH2Cl2 E , C2 , 2σ v C2v
Naphthalene E , C2 , 2C2 , 3σ , i D2h
Chlorobenzene E , C2 , 2σ v C2v
NO2(bent) E , C2 , 2σ v C2v
Cyclopropane E , 2C3 , 3C2 , σ h , 3σ v , 2S3 D3h
CO32− E , 2C3 , 3C2 , σ h , 3σ v , 2S3 D3h
C2H2 E , C∞ , ∞C2 , ∞σ v , σ h , i D∞h

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12-35
Chapter 12: The Chemical Bond Solutions

12.18. The condition for optical activity, and for a molecule to exist in two enantiomeric forms, is that the molecule has neither a plane of
symmetry nor a center of inversion. Can H2O2 exist in two mirror-image forms?
Solution:
Given: H2O2
Required: Can H2O2 exist in two mirror-image forms?
H2O2 belongs to the C2 point group and has neither a plane of symmetry nor a center of inversion. It therefore can exist in two enantiomeric
forms. However, optical activity has not been detected because of the rapid interconversion of the two forms.

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12-36
Chapter 12: The Chemical Bond Solutions

*12.19. Deduce the symmetry species of the following vibrations:

Solution:
Given: Image above
Required: symmetry species

Molecule Point Group Symmetry Species

a. H2 D∞h σ g+
b. H2O C2v a1 , b1 , a1
c. CO2 D∞h σ g+ , σ +u
d. BF3 D3h a1

12-37
Chapter 12: The Chemical Bond Solutions

e. NH3 C3v a1
f. HCN C∞v σ+

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12-38
Chapter 12: The Chemical Bond Solutions

12.20. A molecule having a center of symmetry (i) or having an axis of improper rotation (S) cannot have a dipole moment; all other
molecules can. Note, however, that in tables such as Table 12.3 the symmetry operation S is not always included, since it follows
from other operations (for example, as seen in Figure 12.20, S4 is the product C4σh). The following are molecules that have no center
of symmetry but have no dipole moment:
cyclopropane and cyclopentane
In each case, identify the axis of improper rotation, designate the operation, and relate the operation to the appropriate rotations and
reflections. Which of the point groups in Table 12.3 are such that there can be a dipole moment?
Solution:
Given: cyclopropane and cyclopentane
Required: see above

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12-39
Chapter 12: The Chemical Bond Solutions

*12.21. The spectroscopic properties of several inorganic complexes can be explained in terms of the energy splitting of the five 3d orbitals
as a result of the electron-electron repulsion between the 3d electrons and those on the approaching ligands. In the case of octahedral
complexes like [Fe(CN)6]3+, it is seen that the set of five 3d orbitals on Fe give rise to three symmetry-adapted orbitals of what is
known as T2g symmetry (dxy, dyz, dxz) and two of what is known as Eg symmetry (d z 2 , d x2 − y 2 ). If the coordinate system for analyzing
the energy levels of this complex is set up such that Fe is at the origin and the six ligands approach along the three Cartesian axes
(from the positive and negative sides of each), explain which set of orbitals will have higher energy.
Solution:
Given: [Fe(CN)6]3+
Required: explain which set of orbitals will have higher energy

It is clear from Figure 11.18 that the d z 2 and d x2 − y 2 have lobes pointing along the Cartesian axes while the other three have lobes pointing
between the Cartesian axes. Therefore, if Fe lies at the origin and the ligands lie on the Cartesian axes, the d z 2 and d x2 − y 2 orbitals will
experience most of the electron-electron repulsion. The other three, since their probability density is highest between the Cartesian axes,
experience the repulsive forces to a lesser extent. Therefore, in the presence of the approaching ligands, the set with Eg symmetry
( d z 2 and d x2 − y 2 ) will have higher energy, and the set with T2g symmetry (d xy , d xz , d yz ) will be lower in energy.

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12-40