CHAPTER

38



Molecules and Solids


1*Would you expect the NaCl molecule to be polar or nonpolar?
NaCl is a polar molecule.

2 Would you expect the N
2
molecule to be polar or nonpolar?
N
2
is a non-polar molecule.

3 Does neon occur naturally as Ne or Ne
2
? Why?
Neon occurs naturally as Ne, not Ne
2
. Neon is a rare gas atom with a closed shell electron configuration.

4 What type of bonding mechanism would you expect for (a) HF, (b) KBr, (c) N
2
?
(a) HF - ionic bonding. (b) KBr - ionic bonding. (c) N
2
- covalent bonding.

5* What kind of bonding mechanism would you expect for (a) the N
2
molecule, (b) the KF molecule, (c) Ag atoms in
a solid?
(a) N
2
- covalent bonding. (b) KF - ionic bonding. (c) Ag (solid) - metallic bonding.

6 Calculate the separation of Na
+
and Cl
-
ions for which the potential energy is -1.52 eV.
U
e
= -ke
2
/r; solve for r (see Problem 37-70) r = (1.44/1.52) nm = 0.947 nm


7 The dissociation energy of Cl
2
is 2.48 eV. Consider the formation of an NaCl molecule according to the reaction
Na + 1/2Cl
2

NaCl
Does this reaction absorb energy or release energy? How much energy per molecule is absorbed or released?
Find the net energy change,

E. Note that the

E < 0, therefore energy is released

E = 1.24 eV - (Binding energy of NaCl - see p. 1205)

= (1.24 - 4.27) eV = -3.03 eV
Reaction is exothermic


8 The dissociation energy is sometimes expressed in kilocalories per mole (kcal/mol). (a) Find the relation between
the units eV/molecule and kcal/mol. (b) Find the dissociation energy of molecular NaCl in kcal/mol.
(a) 1 eV/molecule = (1 eV/molecule)(1 kcal/4184 J)(6.02

10
23
molecules/mole)(1.6

10
-19
J/eV) = 23.0 kcal/mol
(b) Dissociation energy of NaCl = (4.27

23) kcal/mol = 98.3 kcal/mol

9* The equilibrium separation of the HF molecule is 0.0917 nm and its measured electric dipole moment is 6.40

10
-30

C

m. What percentage of the bonding is ionic ?

1. Find the dipole moment for 100% ionic bonding
p
100
= er = 1.6

10
-19

9.17

10
-11
C
.
m = 1.47

10
-29
C
.
m
Chapter 38 Molecules and Solids

2. Percent ionic bonding = 100(p
meas
/p
100
) Ionic bonding = 43.6%


10 Do Problem 9 for CsCl, for which the equilibrium separation is 0.291 nm and the measured electric dipole moment
is 3.48

10
-29
C

m.
1. Find the dipole moment for 100% ionic bonding
2. Percent ionic bonding = 100(p
meas
/p
100
)
p
100
= 1.6

10
-19

2.91

10
-10
C
.
m = 4.656

10
-29
C
.
m
Ionic bonding = 74.7%


11 The dissociation energy of LiCl is 4.86 nm and the equilibrium separation is 0.202 nm. The electron affinity of
chlorine is 3.62 eV, and the ionization energy of lithium is 5.39 eV. Determine the core-repulsion energy of LiCl.
1. Determine

E (see Example 38-1)

2. Determine U
e
= -ke
2
/r (see Problem 37-70)
3. Find U
rep
= -(

E + U
e
+ E
d
)

E = (5.39 - 3.62) eV = 1.77 eV

U
e
= -(1.44/0.202) eV = -7.13 eV
U
rep
= -(1.77 - 7.13 + 4.86) eV = 0.50 eV


12 The equilibrium separation of the K
+
and Cl
-
ions in KCl is about 0.267 nm. (a) Calculate the potential energy of
attraction of the ions assuming them to be point charges at this separation. (b) The ionization energy of potassium is
4.34 eV and the electron affinity of Cl is 3.62 eV. Find the dissociation energy neglecting any energy of repulsion. (See
Figure 38-1.) The measured dissociation energy is 4.49 eV. What is the energy due to repulsion of the ions at the
equilibrium separation?
(a) U
e
= -ke
2
/r; ke
2
= 1.44 eV
.
nm
(b) 1. E
d,calc
= -(U
e
+

E)
2. U
rep
= E
d,calc
- E
d,meas

U
e
= -(1.44/0.267) eV = -5.39 eV

E = (4.34 - 3.62) eV = 0.72 eV; E

d,calc
= 4.67 eV
U
rep
= (4.67 - 4.49) eV = 0.18 eV


13* Indicate the mean value of r for two vibration levels in the potential-energy curve for a diatomic molecule and
show that because of the asymmetry in the curve, r
av
increases with increasing vibration energy, and therefore
solids expand when heated.
We shall assume that U(r) is of the form given in
Problem 16 with n = 6. The potential energy curve is
shown in the figure. The turning points for vibrations of
energy E
1
and E
2
are at the values of r where the
energies equal U(r). It is apparent that the average value
of r depends on the energy, and that r
2,av
is greater than
r
1,av
.



14 Calculate the potential energy of attraction between the Na
+
and Cl
-
ions at the equilibrium separation r
0
= 0.236
nm and compare this result with the dissociation energy given in Figure 38-1. What is the energy due to repulsion of
the ions at the equilibrium separation?
1. U
e
= -ke
2
/r
2. Dissociation energy = 4.27 eV
U
e
= -(1.44/0.236) eV = -6.10 eV
U
rep
+

E = (6.10 - 4.27) eV = 1.83 eV

Chapter 38 Molecules and Solids


3.

E = 1.52 eV (see Fig. 38.1); find U

rep
U
rep
= 0.31 eV


15 The equilibrium separation of the K
+
and F
-
ions in KF is about 0.217 nm. (a) Calculate the potential energy of
attraction of the ions, assuming them to be point charges at this separation. (b) The ionization energy of potassium is
4.34 eV and the electron affinity of F is 3.40 eV. Find the dissociation energy neglecting any energy of repulsion. (c)
The measured dissociation energy is 5.07 eV. Calculate the energy due to repulsion of the ions at the equilibrium
separation.
(a) U
e
= -ke
2
/r
(b) E
d,calc
= -(U
e
+

E)
(c) U
rep
= E
d,calc
- E
d,meas

U
e
= -(1.44/0.217) eV = -6.64 eV

E = (4.34 - 3.40) eV = 0.94 eV; E

d,calc
= 5.70 eV
U
rep
= (5.70 - 5.07) eV = 0.63 eV


16 Assume that the core repulsion can be represented by a potential energy of the form U
rep
= C/r
n
. So the total
potential energy is





Use the fact that dU/dr = 0 at r = r
0
, and the results for U
rep
at r = r
0
from Problem 11, to calculate C and n.
With U
rep
= C/r
n
, the repulsive force is F
rep
= -nC/r
n+1
. The electrostatic force of attraction is F
e
= ke
2
/r
2
. At r = r
0
,
the net force is zero. Consequently, nC/r
0
n
= ke
2
/r
0
=
|
U
e
(r
0
)
|
= nU
rep
(r
0
), and n =
|
U
e
(r
0
)/U
rep
(r
0
)
|
. Then the
constant C = U
rep
(r
0
)

r
0
n
.
From Problem 11, U
e
(r
0
) = -7.13 eV and U
rep
(r
0
) = 0.5 eV; so n = 14 .26 and C = 6.21

10
-11
eV
.
nm
-14.26
.


17* (a) Find U
rep
at r = r
0
for NaCl. (b) Assume U
rep
= C/r
n
and find C and n for NaCl. (See Problem 16.)

(a) 1. Find U
e
= -ke
2
/r
0

2. Find U
rep
= -(U
e
+ E
d
+

E)
(b) Using the procedure indicated in Problem 16,
n =
|
U
e
/U
rep|
and C = U
rep
r
0
n

U
e
= -(1.44/0.236) eV = -6.10 eV
U
rep
= -(-6.10 + 4.27 + 1.52) eV = 0.31 eV

n = 19.7; C = 1.37

10
-13
eV
.
nm
-19.7




18 Find other elements with the same subshell electron configuration in the two outermost orbitals as carbon. Would
you expect the same type of hybridization for these elements as for carbon?
Elements similar to carbon in outer shell configurations are silicon, germanium, tin, and lead. We would expect the
same hybridization for these as for carbon, and this is indeed the case for silicon and germanium whose crystal
structure is the diamond structure. Tin and lead, however, are metallic and here the metallic bond is dominant.

19 How does the effective force constant calculated for the CO molecule in Example 38-4 compare with the force
constant of an ordinary spring?
A stiff spring will have a force constant of about 2

10
3
N/m, about the same as the force constant obtained in

E +
r
C
+
r
ke
_ = U
n
2

Chapter 38 Molecules and Solids


Example 38-4.

20 Explain why the moment of inertia of a diatomic molecule increases slightly with increasing angular momentum.
As the angular momentum increases, the separation between the nuclei also increases (the effective force between
the nuclei is similar to that of a stiff spring). Consequently, the moment of inertia also increases.

21* The characteristic rotational energy E
0r
for the rotation of the N
2
molecule is 2.48

10
-4
eV. From this find the
separation distance of the N atoms in N
2
.
1. From Equ. 38-13, I = h
_
2
/2E
0r

2. I = 2M
N
(r/2)
2
= M
N
r
2
/2; M
N
= 14m
p

I = (1.05

10
-34
J
.
s)
2
/7.94

10
-23
J = 1.39

10
-46
J
.
s
2

r = [(2

1.39

10
-46
)/(14

1.67

10
-27
)]
1/2
m = 0.109 nm


22 The separation of the O atoms in O
2
is actually slightly greater than the 0.1 nm used in Example 38-3, and the
characteristic energy of rotation E
0r
is 1.78

10
-4
eV rather than the result obtained in that example. Use this value to
calculate the separation distance of the O atoms in O
2
.
I = M
O
r
2
/2 = h
_
2
/2E
0r
; r = h
_
/ E r 0 O M
r

=

1.05

10
-34
/(16

1.67

10
-27

2.85

10
-23
)
1/2
m

=

0.12 nm


23 Show that the reduced mass is smaller than either mass in a diatomic molecule, and calculate it for (a) H
2
, (b) N
2
,
(c) CO, and (d) HCl. Express your answers in unified mass units.
The reduced mass is given by

= m
1
m
2
/(m
1
+ m
2
) = m
1
/(1 + m
1
/m
2
) = m
2
/(1 + m
2
/m
1
). In each of the latter
expressions the denominator is greater than 1. Consequently,

< m
1
and

< m
2
; Q.E.D.
(a) Here, m
1
= m
2
= 1 u
(b) As in part (a), m
r
= m
1
/2
(c) Let m
1
= 12 u, m
2
= 16 u
(d) Let m
1
= 1 u, m
2
= 35.5 u

= 0.5 u

= 7 u

= 6.86 u

= 0.973 u


24 The equilibrium separation between the nuclei of the LiH molecule is 0.16 nm. Determine the energy separation
between the l = 3 and l = 2 rotational levels of this diatomic molecule.
1. Find

and E
0r
= h
_
2
/2I = h
_
2
/2

r
2

Note: I =

r
2
(see Equ. 38-14)
2. Use Equ. 38-12;

E = 6E
0r

= (6.94/7.94) u = 0.874 u = 1.45

10
-27
kg;
E
0r
=

(1.05

10
-34
)
2
/[2.9

10
-27
(1.6

10
-10
)
2
]

J

=

0.928 meV

E = 5.57 meV


25* Repeat Problem 24 for LiD, where D is the symbol for deuterium. Note that replacing the proton by the
deuteron does not change the equilibrium separation between the nuclei of the molecule.
1. Find

and E
0r
= h
_
2
/2I = h
_
2
/2

r
2

Note: I =

r
2
(see Equ. 38-14)

2. Use Equ. 38-12;

E = 6E
0r

= (2

6.94/8.94) u = 1.55 u = 2.58

10
-27
kg;
E
0r
=

(1.05

10
-34
)
2
/[5.16

10
-27
(1.6

10
-10
)
2
] J


= 0.522

meV

E = 3.13 meV


26 Derive Equations 38-14 and 38-15 for the moment of inertia in terms of the reduced mass of a diatomic molecule.
Let the origin of coordinates be at the point mass m
1
and point mass m
2
be at a distance r
0
from the origin. Then the
Chapter 38 Molecules and Solids


center of mass is at r
CM
= m
2
r
0
/(m
1
+ m
2
). The system rotates about the CM and the distances of m
1
and m
2
from the
CM are r
1
= r
CM
and r
2
= r
0
- r
CM
= m
1
r
0
(m
1
+ m
2
). The moment of inertia about the CM is I = m
1
r
1
2
+ m
2
r
2
2
=
m
1
m
2
r
0
2
/(m
1
+ m
2
) =

r
0
2
; Q.E.D.


27 Use the separation of the K
+
and Cl
-
ions given in Problem 12 and the reduced mass of KCl to calculate the
characteristic rotational energy E
0r
.
Find

and E
0r
= h
_
2
/2I = h
_
2
/2

r
2

Note: I =

r
2
( see Equ. 38-14)

= (39.1

35.5/74.6) u = 18.6 u = 3.09

10
-26
kg;
E
0r
=

(1.05

10
-34
)
2
/[6.18

10
-26
(2.67

10
-10
)
2
] J
= 2.5

10
-24
J = 0.0156 meV


28 The central frequency for the absorption band of HCl shown in Figure 38-17 is at f = 8.66

10
13
Hz, and the
absorption peaks are separated by about

f = 6

10
11
Hz. Use this information, to find (a) the lowest (zero-point)
vibrational energy for HCl, (b) the moment of inertia of HCl, and (c) the equilibrium separation of the atoms.
(a) From Equ. 38-18, E
0
= hf/2
(b) For

l
= 1,

E
l
=
l
h
_
2
/I =
l

h

f; I = h/4

f
(c) I =

r
2
;

= m
H
m
Cl
/(m
H
+ m
Cl
); solve for r
E
0
= (6.63

10
-34

8.66

10
13
/2

1.6

10
-19
) eV = 0.179 eV
I = [6.63

10
-34
/(4

10
11
)] kg
.
m
2
= 2.80

10
-47
kg
.
m
2

= 0.973 u = 1.62

10
-27
kg; r = 0.132 nm


29* Calculate the effective force constant for HCl from its reduced mass and the fundamental vibrational frequency
obtained from Figure 38-17.
From Equ. 38-19, K = 4

f
2
;

= 0.973 u K

=

[4

0.973

1.66

10
-27
(8.66

10
13
)
2
]

N/m

=

480

N/m

30 Two objects of mass m
1
and m
2
are attached to a spring of force constant K and equilibrium length r
0
. (a) Show
that when m
1
is moved a distance

r
1
from the center of mass, the force exerted by
the spring is

r
)
m
m + m
K( = F
1
2
2 1



(b) Show that the frequency of oscillation is f = (1/2

)
K/
0 where

is the reduced mass.

(a) For a two-mass and spring system on which no external forces are acting, the center of mass must remain fixed.
Consequently, if m
1
moves a distance

r
1
from (or toward) the CM, then m
2
must move a distance

r
2
=

r
1
(m
1
/m
2
)
from (or toward) the CM. Then the force exerted by the spring is F = -K

r = -K(

r
1
+

r
2
) = -K

r
1
(m
1
+ m
2
)/m
2
.
(b) From (a) we see that a displacement

r
1
of m
1
results in restoring force F = -K

r
1
(m
1
+ m
2
)/m
2
= -K
eff
r
1
,
where K
eff
= K(m
1
+ m
2
)/m
2
. Writing

= m K 1 eff
/
0 and recalling that

= m
1
m
2
/(m
1
+ m
2
) we obtain

=
K/
0.

Note: In the first printing of the textbook the problem statement for part (b) reads, Show that the angular
frequency of oscillation

The adjective angular should have been omitted.

31 Calculate the reduced mass for the H
35
Cl and H
37
Cl molecules and the fractional difference

. Show that the

Chapter 38 Molecules and Solids


mixture of isotopes in HCl leads to a fractional difference in the frequency of a transition from one rotational state to
another given by

f/f =

. Compute

f/f and compare your result with Figure 38-17.

We shall express the results in unified mass units. For H
35
Cl,

= 35/36 u = 0.9722 U; for H

37
Cl,

= 37/38 u = 0.9737
u. The quantity

= (36

37 - 38

35)/(38

36) = 0.00146. The rotational frequency is proportional to 1/I, where I is the

moment of inertia of the system. Since I is proportional to

, f = C/

and df/f = -d

, or

f/f = -

. For the HCl system,

f/f = -0.00146. From Figure 38-17,

f is about 0.01

10
13
= 10
11
Hz, where f = 8.4

10
13
Hz. Thus

f/f

0.0012, in fair
agreement with the calculated result. (Note that

f is difficult to determine precisely from Figure 38-17.)

32 In calculating the rotational energy levels of a diatomic molecule, we did not consider rotation of the molecule about
the line joining the atoms. (a) Estimate the moment of inertia of the H
2
molecule about this line. (b) Use your results of
(a) to estimate the typical rotational energy E
0r
for rotation about the line joining the atoms. (c) Compare your answer
in (b) with the typical thermal energy kT at T = 300 K.
(a) Assume protons are point particles and the electrons are at a distance of a
0
from the axis.

I = 2m
e
a
0
2

(b) Use Equ. 38-13
(c) at T = 300 K, kT 0.025 eV; E
0r
>> kT

I = 5.1

10
-51
kg
.
m
2

E
0r
= 1.08

10
-18
J = 6.8 eV
Rotation about the axis cannot be excited thermally at
temperatures below the dissociation temperature.


33* Suppose that hard spheres of radius R are located at the corners of a unit cell with a simple cubic structure. (a)
If the hard spheres touch so as to take up the minimum volume possible, what is the size of the unit cell? (b) What
fraction of the volume of the cubic structure is occupied by the hard spheres?
(a) The cube has a length a = 2R
(b) Packing fraction = V
sphere
/V
unit cell

The unit cell is the cube; its volume is 8R
3

Fraction = [(4

R
3
/3)/(8R
3
)] = 0.5236


34 Calculate the distance r
0
between the K
+
and the Cl
-
ions in KCl, assuming that each ion occupies a cubic
volume of side r
0
. The molar mass of KCl is 74.55 g/mol and its density is 1.984 g/cm
3
.
1. Find the volume/mole of KCl
2. V
mol
= 2N
A
r
0
3
since cube length/ion = r
0

V
mol
=
M
/

= (74.55/1.984) cm
3
= 37.58 cm
3

r
0
= (37.58/12.04

10
23
)
1/3
cm = 0.315 nm


35 The distance between the Li
+
and Cl
-
ions in LiCl is 0.257 nm. Use this and the molecular mass of LiCl (42.4
g/mol) to compute the density of LiCl.
1. Find the volume of the unit cell
2. Unit cell has 4 molecules; find mass of unit cell
3. Find the density of solid;

= M
unit cell
/V
unit cell

V
unit cell
= 8(0.257

10
-7
cm)
3
= 1.358

10
-22
cm
3

M
unit cell
= 4(42.4/6.02

10
23
) = 2.82

10
-22
g

= 2.075 g/cm
3


36 Find the value of n in Equation 38-32 that gives the measured dissociation energy of 741 kJ/mol for LiCl, which
has the same structure as NaCl and for which r
0
= 0.257 nm.
1. Use Equs. 38-32 and 38-33 to write
|
U(r
0
)
|

2. Solve for n
7.68 = 1.7476(1.44/0.257)(1 - 1/n)
n = 4.64

Chapter 38 Molecules and Solids

37* Suppose identical bowling balls of radius R are packed into a hexagonal close-packed structure. What fraction
of the available volume of the unit cell is filled by the bowling balls?
In the adjacent drawing we show the base layer of six spheres (solid circles) and
the next layer of spheres (dashed circles) placed in the intersteces. From the
drawing (see also Fig. 38-20) we see that the three spheres of the lower layer
and one of the spheres in the next layer form a regular tetrahedron. The next
layer above the spheres (shown dashed) overlaps the hexagonal layer (shown
solid). It follows that the distance between the layer of solid spheres and that of
the dashed spheres is
a 2/3
, where a = 2R. The unit cell is a cylinder whose
base is the hexagon formed by the centers of the solid spheres and whose height
is the distance between two overlapping layers. The base of the unit cell has an
area of 6(a
2
3
/4) = 3a
2
3
/2 and the height of the unit cell is 2a
2/3
. Thus
the unit cell volume is 3a
3
2
. Each of the six solid spheres on the hexagon is
shared by 3 adjacent unit cells so that these six spheres contribute 2 spheres to
the unit cell. In addition there is the sphere at the center of the base and the
three spheres in the dashed layer. Thus the unit cell contains a total of six
spheres whose total volume is 6[(4

/3)(a
3
/8)] =

a
3
. The volume occupied by
the spheres is therefore

/(3
2
) of the unit cell volume or 0.74 of the unit cell
volume.


38 Which of the following elements are most likely to serve as acceptor impurities in germanium? (a) Bromine, (b)
Gallium, (c) Silicon, (d) Phosphorus, (e) Magnesium.
(b)

39 Which of the following elements are most likely to serve as donor impurities in germanium? (a) Bromine, (b)
Gallium, (c) Silicon, (d) Phosphorus, (e) Magnesium.
(d)

40 What type of semiconductor is obtained if silicon is doped with (a) aluminum and (b) phosphorus? (See Table 37-1
for the electron configurations of these elements.)
(a) p- type (b) n-type

41* What type of semiconductor is obtained if silicon is doped with (a) indium and (b) antimony? (See Table 37-1
for the electron configurations of these elements.)
(a) p-type (b) n-type

42 The donor energy levels in an n-type semiconductor are 0.01 eV below the conduction band. Find the temperature
for which kT = 0.01 eV.

k = 8.62

10
-5
eV/K; T =

E/k T = (10
-2
/8.62

10
-5
) K = 116 K


43 The relative binding of the extra electron in the arsenic atom that replaces an atom in silicon or germanium can be
understood from a calculation of the first Bohr orbit of this electron in these materials. Four of arsenic's outer electrons
Chapter 38 Molecules and Solids


form covalent bonds, so the fifth electron sees a singly charged center of attraction. This model is a modified hydrogen
atom. In the Bohr model of the hydrogen atom, the electron moves in free space at a radius a
0
given by
When an electron moves in a crystal, we
can approximate the effect of the other atoms
by replacing
0
with
0
and m
e
with an
effective mass for the electron. For silicon

is
12 and the effective mass is about 0.2m
e
. For germanium

is 16 and the effective mass is about 0.1m

e
. Estimate the
Bohr radii for the outer electron as it orbits the impurity arsenic atom in silicon and germanium.
Here a
B
= (

m
e
/m
eff
)a
0
Si: a
B
= 31.7 nm; Ge: a
B
= 84.6 nm


44 The ground-state energy of the hydrogen atom is given by

h
2
e mk
=
E
4 2
1
2 2
0
e
4
2
8
m e
=

h


Modify this equation in the spirit of Problem 43 by replacing
0
by
0
and m
e
by an effective mass for the electron to
estimate the binding energy of the extra electron of an impurity arsenic atom in (a) silicon and (b) germanium.
Here E
1
= (m
eff
/m
e
2
)E
0
(a) E
1
= (0.2/144)

13.6 eV = 19 meV
(b) E
1
= (0.1/256)

13.6 eV = 5.3 meV

45* A doped n-type silicon sample with 10
16
electrons per cubic centimeter in the conduction band has a resistivity of
5

10
-3

m at 300 K. Find the mean free path of the electrons. Use the effective mass of 0.2m
e
for the mass of the
electrons. (See Problem 43.) Compare this mean free path with that of conduction electrons in copper at 300 K.

1. Use Equ. 27-8 to find v
av


2. Use Equ. 27-7;

=
e n
m
2
e
av eff v

3. u
F
= 1.57

10
6
m/s (Example 27-4);

= 1.7

10
-8

.
m; n
e
= 8.47

10
28
m
-3

v
av
= 10
2.62 = m/s
5

)
10
0.2(9.11
)(300)
10
3(1.38
31
23
m/s

=
m
) 10 )(1.6 10 )( 10 (5
)
10
)(2.62
11
0.2(9.
2 19 22 3
5 31

= 37.3 nm

Cu
=
m
) 10 )(1.6 10 )(8.47 10 (1.7
)
10
)(1.57
10
(9.11
2 19 28 8
6 31

0 = 38.8
nm

The mean free paths are about the same


46 The measured Hall coefficient of a doped silicon sample is 0.04 V

m/A

T at room temperature. If all the doping

impurities have contributed to the total charge carriers of the sample find (a) the type of impurity (donor or acceptor)
used to dope the sample and (b) the concentration of these impurities.

e m
h
= a
2
0
0
2
e

Chapter 38 Molecules and Solids


(a), (b) R = 1/nq (see Problem 28-70) R > 0, so q > 0, i.e., hole conduction; acceptor impurities
n = 1/Re = 15.6

10
20
m
-3


47 When a pnp junction transistor is used as an amplifier, a small signal in the __________ current results in a large
signal in the __________ current.
(a) collector; base (b) base; collector (c) emitter; base (d) emitter; collector (e) collector; base
(b)

48 When light strikes the p-type semiconductor in a pn junction solar cell,
(a) only free electrons are created.
(b) only positive holes are created.
(c) both electrons and holes are created.
(d) positive protons are created.
(e) none of these is correct.
(c)

49* Simple theory for the current versus the bias voltage across a pn junction yields the equation

1)
e
(
I
= I
/kT eV
0
b


Sketch I versus V
b
for both positive and negative values of V
b
using this equation.
The sketch is shown.
Here we plot I/I
0
versus eV/kT where we have used V
to represent the bias voltage V
b
. Except for the region of
reverse breakdown, this curve is identical to Figure 38-
27.





50 For a temperature of 300 K, use the equation in Problem 49 to find the bias voltage V
b
for which the exponential
term has the value (a) 10 and (b) 0.1.
(a), (b) V
b
= (kT/e) ln(value); k/e = 8.62

10
-5
V/K (a) V
b
= 0.0595 V (b) V
b
= -0.0595 V


51 In Figure 38-34 for the pnp-transistor amplifier, suppose R
b
= 2 k

and R
L
= 10 k

. Suppose further that a 10-

A ac base current generates a 0.5-mA ac collector current. What is the voltage gain of the amplifier?
Voltage gain = i
c
R
L
/i
b
R
b
Voltage gain = 5/0.02 = 250


Chapter 38 Molecules and Solids


52 Germanium can be used to measure the energy of incident particles. Consider a 660-keV gamma ray emitted
from
137
Cs. (a) Given that the band gap in germanium is 0.72 eV, how many electronhole pairs can be generated as
this gamma ray travels through germanium? (b) The number of pairs N in part (a) will have statistical fluctuations
given by
N
. What then is the energy resolution of this detector in this photon energy region?
(a) Number of pairs = E/E
g
= N
(b) Resolution =

E/E =

N/N
N = 9.17

10
5
electron-hole pairs
Resolution = 1/(9.17

10
5
)
1/2
= 1.04

10
-3

0.1%


53* Make a sketch showing the valence and conduction band edges and Fermi energy of a pn-junction diode when
biased (a) in the forward direction and (b) in the reverse direction.
The sketch of the pn junction biased in the (a) forward
and (b) reverse directions is shown below.

The nearly full valence band is shown shaded.
The Fermi level is shown by the dashed line.



54 A "good" silicon diode has the currentvoltage characteristic given in Problem 49. Let kT = 0.025 eV (room
temperature) and the saturation current I
0
= 1 nA. (a) Show that for small reverse-bias voltages, the resistance is 25
M

. Hint: Do a Taylor expansion of the exponential function, or use your calculator and enter small values for V
b
.
(b) Find the dc resistance for a reverse bias of 0.5 V. (c) Find the dc resistance for a 0.5-V forward bias. What is the
current in this case? (d) Calculate the ac resistance dV/dI for a 0.5-V forward bias.
(a) e
x
- 1 = x for x << 1; I

I
0
(eV
b
/kT)
(b) Use Problem 49 expression
(c) Repeat (b) with V
b
= +0.5 V
(d) dV/dI = (dI/dV)
-1
= [(eI
0
/kT)e
eV/kT
]
-1

R = V
b
/I = kT/eI
0
= (0.025/10
-9
)

= 25 M

I = 10
-9
(e
-20
- 1) A = -10
-9
A; R = 0.5

10
9

= 500 M

I = 10
-9
(e
20
- 1) A = 0.485 A; R = (0.5/0.485)

= 1.03

R
ac
= (25 M

)e
-20
= 0.0515

55 A slab of silicon of thickness t = 1.0 mm and width w = 1.0 cm is placed in a magnetic field B = 0.4 T. The slab is
in the xy plane, the magnetic field points in the positive z direction. When a current of 0.2 A flows through the sample
in the positive x direction, a voltage difference of 5 mV develops across the width of the sample with the electric field
in the sample pointing in the positive y direction. Determine the semiconductor type (n or p) and the concentration of
charge carriers.
1. Use Equ. 28-19: n = IB/teV
H

2. See Fig. 28-28; now B points out of the paper
n = [(0.2

0.4)/(10
-3

1.6

10
-19

10
-3
)] m
-3
= 10
23
m
-3

E is in the y direction, therefore carriers are holes; p-type


56 Why would you expect the separation distance between the two protons to be larger in the H
2
+
ion than in the H
2

molecule?
Chapter 38 Molecules and Solids


For H
2
, the concentration of negative charge between the two protons holds the protons together. In the H
2
+
ion,
there is only one electron that is shared by the two positive charges such that most of the electronic charge is again
between the two protons. However, the negative charge in the H
2
+
ion is not as effective as the larger charge in the
H
2
molecule, and the protons should be farther apart. The experimental values support our argument. For H
2
, r
0
=
0.074 nm, while for H
2
+
, r
0
= 0.106 nm.

Note: In the first printing of the textbook the problem statement reads, Why

to be smaller in

? There is no
correct answer to this question since the exact opposite is true.

57* What kind of bonding mechanism would you expect for (a) the HCl molecule (b) the O
2
molecule, (c) Cu atoms
in a solid?
(a) Ionic bonding (b) Covalent bonding (c) Metallic bonding

58 Why does an atom usually absorb radiation only from the ground state whereas a diatomic molecule can absorb
radiation from many different rotational states?
The energy of the first excited state of an atom is orders of magnitude greater than kT at ordinary temperatures.
Consequently, practically all atoms are in the ground state. By contrast, the energy separation between the ground
rotational state and nearby higher rotational states is less than or roughly equal to kT at ordinary temperatures, and
so these higher states are thermally excited and occupied.

59 The equilibrium separation of CsF is 0.2345 nm. If its bonding is 70% ionic, what is its electric dipole moment.
1. p
100
= er
0
; p
exp
= 0.70p
100

p
exp
= (0.70

1.6

2.345

10
-29
) C
.
m = 2.63

10
-29
C
.
m


60 Show that when one atom in a diatomic molecule is much more massive than the other the reduced mass is
approximately equal to the mass of the lighter atom.
From Problem 23,

= m
1
m
2
/(m
1
+ m
2
) = m
1
/(1 + m
1
/m
2
). If m
2
>> m
1
, then m
1
/m
2
<< 1 and so

m
1
.

61* The equilibrium separation between the nuclei of the CO molecule is 0.113 nm. Determine the energy
difference between the l = 2 and l = 1 rotational energy levels of this molecule.
1. Find

and I =

r
0
2

2.

E
1,2
= 2h
_
2
/I

= (16

12/28) u = 6.86 u; I = 1.45

10
-46
kg
.
m
2

E
1,2
= 1.52

10
-22
J = 0.948 meV


62 When a thin slab of semiconducting material is illuminated with monochromatic light most of the light is
transmitted through the slab if the wavelength is greater than 1.85

m. For wavelengths less than 1.85

m, most of
the incident light is absorbed. Determine the energy gap of this semiconductor.
E
g
= hc/

E
g
= (1240/1850) eV = 0.67 eV


63 Show that when an intrinsic semiconductor carries a current in a transverse magnetic field no Hall voltage is
developed across the sample.
In an intrinsic semiconductor, the electron and hole concentrations are equal. Each group of charge carriers
contributes the same Hall voltage, but they are in opposite directions. Consequently, the net voltage is zero.

64 The semiconducting compound CdSe is widely used for light emitting diodes (LEDs). The energy gap in CdSe
is 1.8 eV. What is the frequency of the light emitted by a CdSe LED?
Chapter 38 Molecules and Solids

= hc/E
g

= (1240/1.8) nm = 689 nm (red light)

65* The resistivity of a sample of pure silicon diminishes drastically when it is irradiated with infrared light of
wavelength less than 1.13

m. What is the energy gap of silicon?

E
g
= hc/

E
g
= (1240/1130) eV = 1.10 eV


66 The effective force constant for the HF molecule is 970 N/m. Find the frequency of vibration for this molecule.
Note: We shall assume that the force constant is 970 N/m. (In Problem 30 K
eff
was defined in terms of the
masses.)
From Problem 30, f = (1/2

)
K/
0

= 0.95 u = 1.58

10
-27
kg; f = 1.25

10
14
Hz


67 The frequency of vibration of the NO molecule is 5.63

10
13
Hz. Find the effective force constant for NO.
From Problem 30, K = 4

2
f
2

= 7.47 u = 1.24

10
-26
kg; K = 1550 N/m


68 The force constant of the hydrogen bond in the H
2
molecule is 580 N/m. Obtain the energies of the four lowest
vibrational levels of H
2
, HD, and D
2
molecules, and the wavelengths of photons resulting from transitions between
adjacent vibrational levels of these molecules.
1. Find

for H
2
, HD, and D
2
;

= m
1
m
2
/(m
1
+ m
2
)

2. Use Equs. 38-18 and 38-19; E

= (

+ 1/2)h
_
K/

(H
2
) = 0.837

10
-27
kg;

(HD) = 1.12

10
-27
kg;

(D
2
) = 1.674

10
-27
kg
For the energies, in eV, see the tabulation below.

H
2
HD D
2

0 0.272 eV 0.235 eV 0.192 eV
1 0.814 eV 0.706 eV 0.576 eV
2 1.358 eV 1.176 eV 0.960 eV
3 1.902 eV 1.646 eV 1.344 eV
3.

= hc/

E = (1240 eV
.
nm)/(

E eV)
(H
2
) = 2.28

m;

(HD) = 2.64

m;

(D
2
) = 3.23

m


69* The potential energy between two atoms in a molecule can often be described rather well by the Lenard-Jones
potential, which can be written

1
1
]
1

,
_

,
_

r
a
2
r
a

U
= U
6 12
0

where U
0
and a are constants. Find the interatomic separation r
0
in terms of a for which the potential energy is a
minimum. Find the corresponding value of U
min
. Use Figure 38-4 to obtain numerical values of r
0
and U
0
for the H
2

molecule and express your answers in nanometers and electron volts.

Chapter 38 Molecules and Solids


1. Set dU/dr = 0 and solve for r = r
0


2. From Figure 38-4, r
0
= 0.074 nm, U
min
= -U
0

a =
r
0; =
r
a
12
r
a
12
r
U
=
dr
dU
0
6 12
0
1
1
]
1

,
_

,
_

0

a = 0.074 nm; U
min
= -4.52 eV; U
0
= 4.52 eV


70 In this problem you are to find how the van der Waals force between a polar and a nonpolar molecule depends on
the distance between the molecules. Let the dipole moment of the polar molecule be in the x direction and the
nonpolar molecule be a distance x away.(a) How does the electric field due to an electric dipole depend on distance x
? (b) Use the fact that the potential energy of an electric dipole of moment p in an electric field E is U = -p
E, and
that the induced dipole moment of the nonpolar molecule is proportional to E to find how the potential energy of
interaction of the two molecules depends on separation distance. (c) Using F
x
= - dU/dx find the x dependence of the
force between the two molecules.
(a) From Equ. 22-10, E is proportional to 1/x
3
.
(b) The induced dipole moment is proportional to the field that induces the moment. Hence, p

1/x
3
and the
potential energy of interaction U = -p
.
E

1/x
6
.
(c) F
x
= -dU/dx

1/x
7
.

71 Find the dependence of the force on separation distance between two polar molecules. (See Problem 70.)
In the case of two polar molecules, p does not depend on the field E. Consequently, U

1/x
3
and F
x

1/x
4
.

72 Use the infrared absorption spectrum of HCl in Figure 38-17 to obtain (a) the characteristic rotational energy E
0r
(in
eV) (b) the vibrational frequency f and the vibrational energy hf (in eV).
(a) See Problem 28b and Equs. 38-12 and 38-13
(b) See Problem 28a; hf = 2E
0

E
0r
= h

f/2 = (4.136

10
-15
eV
.
s)(3

10
11
Hz) = 1.24 meV
hf = 2

0.179 eV = 0.358 eV


73* For a molecule such as CO, which has a permanent electric dipole moment, radiative transitions obeying the
selection rule

l
= 1 between two rotational energy levels of the same vibrational level are allowed. (That is, the
selection rule

= 1 does not hold.) (a) Find the moment of inertia of CO and calculate the characteristic
rotational energy E
0r
(in eV). (b) Make an energy level diagram for the rotational levels for
l
= 0 to
l
= 5 for some
vibrational level. Label the energies in electron volts starting with E = 0 for
l
= 0. (c) Indicate on your diagram
transitions that obey

l
= -1 and calculate the energy of the photon emitted (d) Find the wavelength of the
photons emitted for each transition in (c). In what region of the electromagnetic spectrum are these photons?
(a) 1. Find

and I;

= m
1
m
2
/(m
1
+ m
2
); I =

r
0
2

Note: r
0
= 0.113 nm; see Problem 61
2. E
0r
= h
_
2
/2I

= 6.86 u; I = (6.86

1.66

10
-27
)(0.113

10
-9
)
2
kg
.
m
2

= 1.45

10
-46
kg
.
m
2

E
0r
= [(1.05

10
-34
)
2
/2.9

10
-46
] J = 0.238 meV
(b), (c) The energy level diagram is shown in the
adjacent figure. Note that

E
l,l -1
, the energy
difference between adjacent levels for

l
= -
1, is

E
1 , l l
= 2
l

E
0r
.
(d)
l,l -1
= 620/l

E
0r
;

in nm and E
0r
in eV. We



Chapter 38 Molecules and Solids


h
h
find:

1,0
= 2605

m;
2,1
= 1303

m;
3,2
= 868

m;

4,3
= 651

m;
5,4
= 521

m
These wavelengths fall in the microwave region
of the spectrum.



74 Use the results of Problem 16 to calculate the vibrational frequency of the LiCl molecule. To do this, expand the
potential about r = r
0
where r
0
is the equilibrium separation, in a Taylor series. Retain only the term proportional to
(r-

r
0
)
2
. Recall that the potential energy of a simple harmonic oscillator is given by V = 1/2m

2
x
2
. What is the
wavelength resulting from transitions between adjacent harmonic oscillator levels of this molecule?
From Problem 16 we have U(r) = -(ke
2
/r) + C/r
n
, neglecting the constant term

E. Also, nU
rep
(r
0
) = ke
2
/r
0
= nC/r
0
n
.
The constant C = U
rep
(r
0
)r
0
n
. So, C/r
n
= ke
2
r
0
n-1
/nr
n
. We now let r = r
0
+

, where

<< r
0
. Using the binomial
expansion one can write r
n
= r
0
n
+ n

r
0
n-1
+ n(n - 1)

2
r
0
n-2
/2 +
. . .
. Then C/r
n
= ke
2
/[nr
0
(1 + n

/r
0
+ n(n - 1)

2
/2r
0
2
)]
for r = r
0
+

. Next, using (1 +

)
-1
= 1 -

2
+
. . .
and keeping only terms of order (

/r
0
)
2
, we can write -(ke
2
/r) =
-(ke
2
/r
0
)[1 -

/r
0
+ (

/r
0
)
2
] and C/r
n
= (ke
2
/nr
0
)[1 - n

/r
0
+ n(n + 1)

2
/2r
0
2
]. To lowest order in

/r
0
the potential
energy is U = U
0
+ (ke
2
/2r
0
3
)[(n + 1)

2
]. We now set (ke
2
/2r
0
3
)[(n + 1)

2
] = 1/2m

2
and solve for

. We obtain

= r
/m
e
k 1) + (n
3
0
2
.
For the specific case of LiCl, we must use the reduced mass

= 6.94

35.5/42.44 u = 5.81 u for m, r

0
= 0.202 nm,
and set n = 14.26 The result is f = 2.11

10
14
s
-1
and

E = = 0.139 eV. Thus

= 1240/0.139 nm = 8.93

m.

75 Repeat Problem 74 for the NaCl molecule.
We use the result of the preceding problem;

= r
/m
e
k 1) + (n
3
0
2
.
For NaCl we must use the reduced mass

= 23

35.5/58.5 u = 13.96 u for m, r

0
= 0.236 nm, and n = 19.7. We then
find that f = 1.25

10
14
s
-1
and

E = = 0.0826 eV. Thus

= 1240/0.0821 nm = 15.1

m

76 A one-dimensional model of an ionic crystal consists of a line of alternating positive and negative ions with distance
r
0
between each ion. (a) Show that the potential energy of attraction of one ion in the line is
Chapter 38 Molecules and Solids




,
_

... + +
r
ke
2
= V
0
2
5
1
4
1
3
1
2
1
1


(b) Using the result that

... +
4
x
3
x
+
2
x
x = x) + (
4 3 2
1 ln


show that the Madelung constant for this one-dimensional model is

= 2 ln 2 = 1.386.

(a) The figure shows the one dimensional model.
Here the open and shaded circles represent ions
of charges +e and -e, respectively. The
separation between adjacent ions is r
0
. We can
now write the potential energy of the ion at
position 0.



,
_

K K + +
r
ke
= +
r
ke
r
ke
+
r
ke
V =
5
1
4
1
3
1
2
1
1
2
3
2
2
2 2
0
2
0
2
0
2
0
2
0.

(b) Note that when x = 1, the expansion for ln(1 + x) is just equal to the series in the parenthesis above. Therefore,
we can write V = -(ke
2
/r
0
)(2 ln 2). From the definition of the Madelung constant, Equ. 38-27,

= 2 ln 2 = 1.386.