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43

Molecules and Solids


CHAPTER OUTLINE
43.1
43.2
43.3
43.4
43.5
43.6

43.7
43.8

Molecular Bonds
Energy States and Spectra
of Molecules
Bonding in Solids
Free-Electron Theory of
Metals
Band Theory of Solids
Electrical Conduction in
Metals, Insulators, and
Semiconductors
Semiconductor Devices
Superconductivity

ANSWERS TO QUESTIONS
Q43.1

Rotational, vibrational and electronic (as discussed in


Chapter 42) are the three major forms of excitation. Rotational
2

, where I is
2I
the moment of inertia of the molecule. A typical value for a
small molecule is on the order of 1 meV = 10 3 eV . Vibrational
energy is on the order of hf, where f is the vibration frequency
of the molecule. A typical value is on the order of 0.1 eV.
Electronic energy depends on the state of an electron in the
molecule and is on the order of a few eV. The rotational energy
can be zero, but neither the vibrational nor the electronic
energy can be zero.
energy for a diatomic molecule is on the order of

Q43.2

The Pauli exclusion principle limits the number of electrons in


the valence band of a metal, as no two electrons can occupy the
same state. If the valence band is full, additional electrons must
be in the conduction band, and the material can be a good
conductor. For further discussion, see Q43.3.

Q43.3

The conductive properties of a material depend on the electron population of the conduction band
of the material. If the conduction band is empty and a full valence band lies below the conduction
band by an energy gap of a few eV, then the material will be an insulator. Electrons will be unable to
move easily through the material in response to an applied electric field. If the conduction band is
partly full, states are accessible to electrons accelerated by an electric field, and the material is a good
conductor. If the energy gap between a full valence band and an empty conduction band is
comparable to the thermal energy k B T , the material is a semiconductor.

Q43.4

Thermal excitation increases the vibrational energy of the molecules. It makes the crystal lattice less
orderly. We can expect it to increase the width of both the valence band and the conduction band, to
decrease the gap between them.

545

546

Molecules and Solids

Q43.5

First consider electric conduction in a metal. The number of conduction electrons is essentially fixed.
They conduct electricity by having drift motion in an applied electric field superposed on their
random thermal motion. At higher temperature, the ion cores vibrate more and scatter more
efficiently the conduction electrons flying among them. The mean time between collisions is
reduced. The electrons have time to develop only a lower drift speed. The electric current is
reduced, so we see the resistivity increasing with temperature.
Now consider an intrinsic semiconductor. At absolute zero its valence band is full and its
conduction band is empty. It is an insulator, with very high resistivity. As the temperature increases,
more electrons are promoted to the conduction band, leaving holes in the valence band. Then both
electrons and holes move in response to an applied electric field. Thus we see the resistivity
decreasing as temperature goes up.

Q43.6

In a metal, there is no energy gap between the valence and conduction bands, or the conduction
band is partly full even at absolute zero in temperature. Thus an applied electric field is able to inject
a tiny bit of energy into an electron to promote it to a state in which it is moving through the metal
as part of an electric current. In an insulator, there is a large energy gap between a full valence band
and an empty conduction band. An applied electric field is unable to give electrons in the valence
band enough energy to jump across the gap into the higher energy conduction band. In a
semiconductor, the energy gap between valence and conduction bands is smaller than in an
insulator. At absolute zero the valence band is full and the conduction band is empty, but at room
temperature thermal energy has promoted some electrons across the gap. Then there are some
mobile holes in the valence band as well as some mobile electrons in the conduction band.

Q43.7

Ionic bonds are ones between oppositely charged ions. A simple model of an ionic bond is the
electrostatic attraction of a negatively charged latex balloon to a positively charged Mylar balloon.
Covalent bonds are ones in which atoms share electrons. Classically, two children playing a
short-range game of catch with a ball models a covalent bond. On a quantum scale, the two atoms are
sharing a wave function, so perhaps a better model would be two children using a single hula hoop.
Van der Waals bonds are weak electrostatic forces: the dipole-dipole force is analogous to the
attraction between the opposite poles of two bar magnets, the dipoleinduced dipole force is
similar to a bar magnet attracting an iron nail or paper clip, and the dispersion force is analogous to
an alternating-current electromagnet attracting a paper clip.
A hydrogen atom in a molecule is not ionized, but its electron can spend more time elsewhere
than it does in the hydrogen atom. The hydrogen atom can be a location of net positive charge, and
can weakly attract a zone of negative charge in another molecule.

Q43.8

Ionically bonded solids are generally poor electric conductors, as they have no free electrons. While
they are transparent in the visible spectrum, they absorb infrared radiation. Physically, they form
stable, hard crystals with high melting temperatures.

Q43.9

Covalently bonded solids are generally poor conductors, as they form structures in which the atoms
share several electrons in the outer shell, leaving no room for conducting electrons. Depending on
the structure of the solid, they are usually very hard and have high melting points.

Q43.10

Metals are good conductors, as the atoms have many free electrons in the conduction band. Metallic
bonds allow the mixing of different metals to form alloys. Metals are opaque to visible light, and can
be highly reflective. A metal can bend under stress instead of fracturing like ionically and covalently
bonded crystals. The physical properties vary greatly depending on the composition.

Chapter 43

547

Q43.11

The energy of the photon is given to the electron. The energy of a photon of visible light is sufficient
to promote the electron from the lower-energy valence band to the higher-energy conduction band.
This results in the additional electron in the conduction band and an additional holethe energy
state that the electron used to occupyin the valence band.

Q43.12

Along with arsenic (As), any other element in group V, such as phosphorus (P), antimony (Sb), and
bismuth (Bi), would make good donor atoms. Each has 5 valence electrons. Any element in group III
would make good acceptor atoms, such as boron (B), aluminum, (Al), gallium (Ga), and indium (In).
They all have only 3 valence electrons.

Q43.13

The two assumptions in the free-electron theory are that the conduction electrons are not bound to
any particular atom, and that the nuclei of the atoms are fixed in a lattice structure. In this model, it
is the soup of free electrons that are conducted through metals. The energy band model is more
comprehensive than the free-electron theory. The energy band model includes an account of the
more tightly bound electrons as well as the conduction electrons. It can be developed into a theory
of the structure of the crystal and its mechanical and thermal properties.

Q43.14

A molecule containing two atoms of 2 H, deuterium, has twice the mass of a molecule containing
two atoms of ordinary hydrogen 1 H . The atoms have the same electronic structure, so the molecules
have the same interatomic spacing, and the same spring constant. Then the moment of inertia of the
double-deuteron is twice as large and the rotational energies one-half as large as for ordinary
1
times that of H 2 .
hydrogen. Each vibrational energy level for D 2 is
2

Q43.15

Rotation of a diatomic molecule involves less energy than vibration. Absorption of microwave
photons, of frequency ~ 10 11 Hz , excites rotational motion, while absorption of infrared photons, of
frequency ~ 10 13 Hz , excites vibration in typical simple molecules.

Q43.16

Yes. A material can absorb a photon of energy greater than the energy gap, as an electron jumps into
a higher energy state. If the photon does not have enough energy to raise the energy of the electron
by the energy gap, then the photon will not be absorbed.

Q43.17

From the rotational spectrum of a molecule, one can easily calculate the moment of inertia of the
molecule using Equation 43.7 in the text. Note that with this method, only the spacing between
adjacent energy levels needs to be measured. From the moment of inertia, the size of the molecule
can be calculated, provided that the structure of the molecule is known.

SOLUTIONS TO PROBLEMS
Section 43.1

P43.1

Molecular Bonds
q2

e1.60 10 j e8.99 10 j N =
=
e5.00 10 j
19 2

0.921 10 9 N toward the other ion.

(a)

F=

(b)

1.60 10 19 8.99 10 9
q 2
=
U=
J 2.88 eV
4 0 r
5.00 10 10

4 0 r 2

10 2

je
2

548
P43.2

Molecules and Solids

We are told

K + Cl + 0.7 eV K + + Cl

and

Cl + e Cl + 3.6 eV

or

Cl Cl + e 3.6 eV .

By substitution,

K + Cl + 0.7 eV K + + Cl+e 3.6 eV


K + 4.3 eV K + +e

or the ionization energy of potassium is 4.3 eV .


P43.3

(a)

Minimum energy of the molecule is found from

LM OP .
N Q
B O
L1 1 O B =

= M P
P
2 A B PQ
N4 2Q A

dU
2A
= 12 Ar 13 + 6Br 7 = 0 yielding r0 =
dr
B
(b)

E = U r = U r = r = 0
0

LM A
MN 4 A B
2

16

B2
4A

This is also the equal to the binding energy, the amount of energy given up by the two
atoms as they come together to form a molecule.

(c)

L 2e0.124 10
r =M
MN 1.488 10
e1.488 10
E=
4e0.124 10

120

60

60

(a)

eV m6

eV m6

120

*P43.4

eV m12

j OP
PQ

16

= 7.42 10 11 m = 74.2 pm

eV m12

= 4.46 eV

We add the reactions K + 4.34 eV K + + e


and

I + e I + 3.06 eV

to obtain

K + I K + + I + 4.34 3.06 eV .

The activation energy is 1.28 eV .

(b)

LM FG IJ
MN H K

dU 4
=
12

dr
r

At r = r0 we have

= 2 1 6
r0

13

+6

FG IJ OP
H r K PQ
7

FG IJ
H K

dU

= 0 . Here
dr
r0

13

FG IJ
H K

1
2 r0

= 2 1 6 0.305 nm = 0.272 nm = .

Then also

LF 2 r I F 2 r I OP
L1 1 O
G
+ E = 4 M P + E
U br g = 4 MG
J
J
r
r
MNH
N4 2Q
K H
K PQ
= E U br g = 1.28 eV + 3.37 eV = 4.65 eV =
1 6

continued on next page

12

1 6
0

= + Ea

Chapter 43

(c)

af

F r =

LM FG IJ
MN H K

dU 4
=
12

dr
r

13

FG IJ OP
H r K PQ
7

To find the maximum force we calculate

rrupture
Fmax =

FG 42 IJ
H 156 K

LM
MN

f LM FG IJ
MN H K

= 6.55 nN

13 6

FG IJ
H K

dF 4
=
156
dr 2
r

16

4 4.65 eV
42
12
0.272 nm
156

549

14

+ 42

FG IJ OP = 0 when
H r K PQ
8

FG 42 IJ OP = 41.0 eV nm = 41.0 1.6 10


H 156 K PQ
10
76

19

Nm
m

Therefore the applied force required to rupture the molecule is +6.55 nN away from the
center.

(d)

LF
LMF I F I OP
I F I
GMH r + s JK GH r + s JK P + E = 4 MMGH 2r + rs JK GH r2 + s JK
N
Q
N
L 1 F s I 1 F s I OP
= 4 M G1 + J
MN 4 H r K 2 GH1 + r JK PQ + E
L 1 F s s I 1 F1 6 s + 21 s I OP + E
= 4 M G 1 12 + 78
MN 4 H r r JK 2 GH r r JK PQ
12

U r0 + s = 4

1 6

12

where k =

P43.5

2
0

s
s2
s
s2
+ 78 2 2 +12 42 2 + Ea +
r0
r0
r0
r0

= + E a + 0

g b g

OP
PQ + E

2
0

U r0 + s U r0 +

1 6

=12

12

FG s IJ + 36 s
Hr K
r

2
0

1 2
ks
2

72 72 4.65 eV
=
= 3 599 eV nm 2 = 576 N m .
2
r02
0.305 nm

At the boiling or condensation temperature,

k BT 10 3 eV = 10 3 1.6 10 19 J
T

1.6 10 22 J
~ 10 K .
1.38 10 23 J K

550

Molecules and Solids

Section 43.2
P43.6

Energy States and Spectra of Molecules

fe

132.9 126.9
m1 m 2
=
1.66 10 27 kg = 1.08 10 25 kg
m1 + m 2 132.9 + 126.9

je

I = r 2 = 1.08 10 25 kg 0.127 10 9 m

E=

(a)

a f

I
1 2
I =
2
2I

J = 0 gives E = 0

= 1.74 10 45 kg m 2

J J +1
2I

e6.626 10
=
4 e1.74 10

J = 1 gives E =

a f

34

Js

45

kg m 2

= 6.41 10 24 J = 40.0 eV

hf = 6.41 10 24 J 0 to f = 9.66 10 9 Hz
f=

(b)
P43.7

2
E1
h
=
=
r 2
h
hI 4 2 r 2

If r is 10% too small, f is 20% too large.

For the HCl molecule in the J = 1 rotational energy level, we are given
r0 = 0.127 5 nm.
Erot =
Taking J = 1 , we have

a f

J J +1

2I

Erot =

1 2
I or =
2

2 2
= 2 .
I
I2

The moment of inertia of the molecule is given by Equation 43.3.


m1 m 2
I = r02 =
r02
m1 + m 2
2
0

Therefore, = 2

P43.8

hf = E =
I=

4 h 2
2 hf

2I

fe

h
2

2 f

2I

a f

1 1+1 =

2I

a 4f

6.626 10 34 J s
2

= 2.62 10 47 kg m 2 .

1.055 10 34 J s
= 5.69 10 12 rad s .
2
47
2.62 10
kg m

= 2

a f

je

= 0.972 u 1.66 10 27 kg u 1.275 10 10 m

2 2+1

FIG. P43.7

IJ
K

FG
H
L a1 ufa35 uf OPr
I=M
N 1 u + 35 u Q

e2.30 10

11

Hz

= 1.46 10 46 kg m 2

Chapter 43

P43.9

I = m1 r12 + m 2 r22

m1 r1 = m 2 r2

and

r1 + r2 = r .

Then r1 =

m 2 r2
m1

so

m 2 r2
+ r2 = r
m1

and

r2 =

m1 r
.
m1 + m 2

Also, r2 =

m1 r1
.
m2

Thus,

r1 +

m1 r1
=r
m2

and

r1 =

m2r
m1 + m 2

I = m1

P43.10

where

bm

m 22 r 2

m 2 m12 r 2

m1 m 2 r 2 m 2 + m1

g=m m r
1

g bm + m g
bm + m g
22.99a35.45f
=
a22.99 + 35.45f e1.66 10 kgj = 2.32 10 kg
I = r = e 2.32 10
kg je0.280 10 mj = 1.81 10
+ m2

m1 + m 2

27

(a)

= r2 .

26

26

45

kg m 2

a f 2 I 1a1 + 1f = 3 I I = 2 I = 42h I
2I
kg m j
c 4 I e3.00 10 m sj4 e1.81 10
=
=
= 1.62 cm
2h
J sj
2e6.626 10
F I
The energy of a rotational transition is E = G J J where J is the rotational quantum number of the
HIK
hc

(b)

2 2+1

45

34

P43.11

551

higher energy state (see Equation 43.7). We do not know J from the data. However,
E =

hc

e6.626 10

34

je

J s 3.00 10 8 m s

j F 1 eV I .
GH 1.60 10 J JK
19

For each observed wavelength,

(mm)
0.120 4
0.096 4
0.080 4
0.069 0
0.060 4

E (eV)
0.010 32
0.012 88
0.015 44
0.018 00
0.020 56

The Es consistently increase by 0.002 56 eV.

and I =

E1

e1.055 10 J sj F 1 eV I =
=
b0.002 56 eVg GH 1.60 10 J JK
34

E1 =

= 0.002 56 eV

19

For the HCl molecule, the internuclear radius is

2.72 10 47 kg m 2 .

r=

2.72 10 47
m = 0.130 nm.
1.62 10 27

552
P43.12

Molecules and Solids

(a)

Minimum amplitude of vibration of HI is

(b)

1 2 1
kA = hf :
2
2

A=

For HF,

A=

e6.626 10

hf
=
k

34

je

J s 6.69 10 13 s

320 N m

e6.626 10

34

je

J s 8.72 10 13 s

970 N m

j = 1.18 10

j = 7.72 10

12

11

m = 0.011 8 nm .

m = 0.007 72 nm .

Since HI has the smaller k, it is more weakly bound.


P43.13

m1 m 2
35
=
1.66 10 27 kg = 1.61 10 27 kg
m1 + m 2 36

Evib =

P43.14

(a)

k
= 1.055 10 34

480
= 5.74 10 20 J = 0.358 eV
1.61 10 27

a16 ufa16 uf
a16 uf + a16 uf = 8 u = 8e1.66 10 kg j = 1.33 10 kg .
The moment of inertia is then I = r = e1.33 10
kg je1.20 10 mj = 1.91 10
kg m .
27

The reduced mass of the O 2 is =

26

(b)

10

e1.055 10
=
J a J + 1f =
2I
2e1.91 10
= e 2.91 10
Jj J a J + 1f .
2

26

j J a J + 1f .
kg m j

34

Js

The rotational energies are

Erot

Thus

Erot

And for J = 0 , 1, 2 ,

Erot = 0 , 3.64 10 4 eV, 1.09 10 3 eV .

FG
H

1
2

FG
H

1
1 eV
3.14 10 20 J
2
1.60 10 19

Evib = v +

Evib = v +

IJ
K
IJ e
K

FG
H

= v+

IJ e
K

46

23

j 8e1.166177 10N mkgj


IJ = FG v + 1 IJ a0.196 eVf
2K
JK H

1
1.055 10 34 J s
2

jFGH

For v = 0 , 1, 2 , E vib = 0.098 2 eV, 0.295 eV, 0.491 eV .

27

46

Chapter 43

P43.15

553

In Benzene, the carbon atoms are each 0.110 nm from the axis and each hydrogen atom is
0.110 + 0.100 nm = 0.210 nm from the axis. Thus, I = mr 2 :

je

j + 6e1.67 10

I = 6 1.99 10 26 kg 0.110 10 9 m

27

je

kg 0.210 10 9 m

= 1.89 10 45 kg m 2 .

The allowed rotational energies are then


Erot
Erot

e1.055 10 J sj Ja J + 1f = e2.95 10 Jj Ja J + 1f = e18.4 10


=
J a J + 1f =
2I
kg m j
2e1.89 10
= b18.4 eV g J a J + 1f where J = 0 , 1, 2 , 3 ,
2

34

24

45

ja f

eV J J + 1

The first five of these allowed energies are: Erot = 0 , 36.9 eV, 111 eV, 221 eV, and 369 eV .
*P43.16

We carry extra digits through the solution because part (c) involves the subtraction of two close
numbers. The longest wavelength corresponds to the smallest energy difference between the
rotational energy levels. It is between J = 0 and J = 1 , namely

hc
hc
4 2 Ic
= 2 =
. If is the reduced mass, then
Emin
h
I

j = e1.624 605 10
m j e 2.997 925 10

I = r 2 = 0.127 46 10 9 m
=

4 2 1.624 605 10 20

20

ms

6.626 075 10 34 J s

35 =

(a)

m2

j = e2.901 830 10

b1.007 825ugb34.968 853ug = 0.979 593u = 1.626 653 10

27

1.007 825u + 34.968 853 u

je

23

m kg

kg

From (1): 35 = 2.901 830 10 23 m kg 1.626 653 10 27 kg = 472 m

37 =

(b)

b1.007 825ugb36.965 903ug = 0.981 077u = 1.629 118 10

27

1.007 825u + 36.965 903 u

je

kg

From (1): 37 = 2.901 830 10 23 m kg 1.629 118 10 27 kg = 473 m

37 35 = 472.742 4 m 472.027 0 m = 0.715 m

(c)
P43.17

hf =

h2
4 2 I

J where the rotational transition is from J 1 to J,

where f = 6.42 10 13 Hz and I = 1.46 10 46 kg m 2 from Example 43.1.

je

46
2
kg m 2 6.42 10 13 s
4 2 If 4 1.46 10
=
= 558
J=
h
6.626 10 34 J s

(1)

554
*P43.18

Molecules and Solids

We find an average spacing between peaks by counting 22 gaps between 7.96 10 13 Hz and
9.24 10 13 Hz :
f =
I=

*P43.19

a9.24 7.96f10

13

Hz

= 0.058 2 10 13 Hz =

22
h

4 2 f

F
GH

1 h2
h 4 2 I

I
JK

6.63 10 34 J s
= 2.9 10 47 kg m 2
4 2 5.82 10 11 s

We carry extra digits through the solution because the given wavelengths are close together.
(a)

FG
H

IJ
K

2
1
hf +
J J +1
2
2I

EvJ = v +

a f

1
hf ,
2

E00 =

E11 E00 = hf +

hf +

2
I

2
I

(b)

je

34

J s 2.997 925 10 8 m s

2.211 2 10

hc

(1)

e6.626 075 10

34

je

J s 2.997 925 10 8 m s

2.405 4 10

3
I

= 7.252 89 10 21 J

3 1.054 573 10 34 J s
7.252 89 10 21 J

(2)

= 4.60 10 48 kg m 2

From (1):
f=

e1.054 573 10 J sj

J s e 4.600 060 10
kg m je6.626 075 10
34

8.983 573 10 20 J
6.626 075 10 34

48

= 1.32 10 14 Hz
(c)

= 8.258 284 10 20 J

Subtract (2) from (1):

I =

e6.626 075 10
=

hc

= 8.983 573 10 20 J

E11 E02 = hf

hf

2
3
1
3 2
, E02 = hf +
hf +
I
I
2
2

E11 =

I = r 2 , where is the reduced mass:

1
1
m H = 1.007 825u = 8.367 669 10 28 kg .
2
2

So r =

4.600 060 10 48 kg m 2
8.367 669 10 28 kg

= 0.074 1 nm .

34

Js

Chapter 43

P43.20

The emission energies are the same as the absorption energies, but the final state must be below
v = 1, J = 0 . The transition must satisfy J = 1 , so it must end with J = 1 . To be lower in energy, it

must be v = 0 , J = 1 . The emitted photon energy is therefore

hf photon = Evib

v =1

+ Erot

J =0

j eE

vib v = 0

+ Erot

J =1

j = eE

vib v =1

Evib

v=0

j eE

Erot

rot J = 1

J =0

hf photon = hf vib hfrot


Thus, fphoton = f vib frot = 6.42 10 13 Hz 1.15 10 11 Hz = 6.41 10 13 Hz .
P43.21

Ix =

The moment of inertia about the molecular axis is

2
2
2
4
mr 2 + mr 2 = m 2.00 10 15 m .
5
5
5

The moment of inertia about a perpendicular axis is I y = m


The allowed rotational energies are Erot =
E1 =
E1 , x
E1 , y

Section 43.3
P43.22

FG R IJ
H 2K

+m

FG R IJ
H 2K

2
m
2.00 10 10 m .
2

F I Ja J + 1f , so the energy of the first excited state is


GH 2 I JK
2

. The ratio is therefore

e
=
e

2
2

j = I = b1 2gme2.00 10
I j I
b4 5gme2.00 10
Ix

y
x

10
15

j
mj

2
2

5
10 5
8

e j

= 6.25 10 9 .

Bonding in Solids

Consider a cubical salt crystal of edge length 0.1 mm.

F 10 m I ~ 10 .
GH 0.261 10 m JK
e10 mj FGH 0.26110 10m m IJK ~ 10
3

The number of atoms is

17

This number of salt crystals would have volume

m3 .

If it is cubic, it has edge length 40 m.

P43.23

P43.24

555

FG
H

IJ b
K

j ee

j FG 1 1 IJ = 1.25 10
j H 8K

1.60 10 19
ke e2
1
9
= 1.747 6 8.99 10
U=
1
r0
m
0.281 10 9

ge

18

J = 7.84 eV

Visualize a K + ion at the center of each shaded cube, a Cl ion at the center
of each white one.
The distance ab is
Distance ac is
Distance ad is

2 0.314 nm = 0.444 nm .

2 0.314 nm = 0.628 nm .
22 +

e 2 j a0.314 nmf =
2

0.769 nm .

FIG. P43.24

556
P43.25

Molecules and Solids

ke e2 ke e2 ke e2 ke e2 ke e2 ke e2 ke e2 ke e2

+
+

+
+

2r
2r
3r
3r
4r
4r
r
r
2k e 2
1 1 1
= e
1 + +
2 3 4
r

e e e e e e
+ + +

U=

FG
IJ
H
K
x
x
x
But, lna1 + xf = 1
+

+
2
3
4
2

so, U =

2r
3r

FIG. P43.25

2kee
e
ln 2 , or U = k e
where = 2 ln 2 .
r
r

Section 43.4

Free-Electron Theory of Metals

Section 43.5

Band Theory of Solids

P43.26

FG IJ
H K

23

h 2 3n e
EF =
2 m 8

L
e6.626 10 J sj
=M
MM 2e9.11 10 kg je1.60 10
N

34

31

19

OPF 3 I
G J
J eV j PH 8 K
QP

23

n e2 3

EF = 3.65 10 19 n e2 3 eV with n measured in electrons m3 .


P43.27

The density of conduction electrons n is given by EF =

or

FG
H

8 2mEF
ne =
3
h2

IJ
K

32

ja fe

n Ag = 10.6 10 3 kg m3
So an average atom contributes
(a)

3 2

= 5.80 10 28 m 3 .

atom I F
1u
J
jFGH 1108
u K GH 1.66 10

27

I = 5.91 10
J
kg K

28

m 3 .

5.80
= 0.981 electron to the conduction band .
5.91

1
mv 2 = 7.05 eV
2
v=

(b)

23

31
kg 5.48 1.60 10 19 J
8 2 9.11 10
=
3
3
6.626 10 34 J s

The number-density of silver atoms is

P43.28

FG IJ
H K

h 2 3n e
2 m 8

fe

2 7.05 eV 1.60 10 19 J eV
9.11 10

31

kg

j=

1.57 10 6 m s

Larger than 10 4 m s by ten orders of magnitude. However, the energy of an electron at


room temperature is typically k BT =

1
eV .
40

Chapter 43

P43.29

557

For sodium, M = 23.0 g mol and = 0.971 g cm3 .

je

6.02 10 23 electrons mol 0.971 g cm 3


NA
=
ne =
23.0 g mol
M

(a)

n e = 2.54 10 22 electrons cm3 = 2.54 10 28 electrons m3

(b)

P43.30

EF

F h I FG 3n IJ
=G
H 2m JK H 8 K
2

23

e6.626 10
=
2e9.11 10

34
31

j LM 3e2.54 10
8
kg j M
N
2

Js

28

m 3

j OP
PQ

23

= 5.05 10 19 J = 3.15 eV

The melting point of silver is 1 234 K. Its Fermi energy at 300 K is 5.48 eV. The approximate fraction
of electrons excited is

e
a

jb

g
j

1.38 10 23 J K 1 234 K
k BT
=
2% .
EF
5.48 eV 1.60 10 19 J eV
P43.31

fe

Taking EF = 5.48 eV for sodium at 800 K,


f = eb

E EF k B T

e b E EF g

k BT

+1

= 0.950

1
1 = 0.052 6
0.950

E EF
= ln 0.052 6 = 2.94
k BT

e1.38 10 ja800f J = 0.203 eV or


= 2.94
23

E EF

P43.32

1.60 10 19 J eV

d = 1.00 mm , so

V = 1.00 10 3 m

The density of states is

g E = CE 1 2 =

af

af

gE =

or

E = 5.28 eV .

= 1.00 10 9 m 3 .

8 2 m 3 2
h

E1 2

8 2 9.11 10 31 kg

e6.626 10

34

Js

3 2

a4.00 eVfe1.60 10

19

J eV

af

g E = 8.50 10 46 m 3 J 1 = 1.36 10 28 m 3 eV 1 .
So, the total number of electrons is

a fa f e

jb

ge

N = g E E V = 1.36 10 28 m 3 eV 1 0.025 0 eV 1.00 10 9 m3 = 3.40 10 17 electrons .

558
P43.33

Molecules and Solids

Eav =

af

1
EN E dE
ne 0

af

af

Since f E = 1 for E < EEF and f E = 0 for E > EF , we can take


Eav =

EF

1
ne

CE 3 2 dE =

EF

C
ne

2C 5 2
EF .
5n e

E 3 2 dE =

But from Equation 43.24,


P43.34

af
N aEf = CE

N E = 0 for E > EF ;.

At T = 0 ,

C 3 3 2
= EF , so that
ne 2

Eav =

12

8 2 m e3 2
h3

FG 2 IJ FG 3 E IJ E
H 5KH 2 K
3 2
F

5 2
F

E1 2

3
EF .
5

Consider first the wave function in x. At x = 0 and x = L , = 0.


Therefore,

sin k x L = 0

and

k x L = , 2 , 3 , .

Similarly,

sin k y L = 0

and

k y L = , 2 , 3 ,

sin k z L = 0

and

k z L = , 2 , 3 ,

FG n x IJ sinFG n y IJ sinFG n z IJ .
H L K H L K H L K
2m
+
+
=
From
aU Ef ,
x
y
z
F n n n I = 2m E
a f
GH L L L JK

= A sin

2
x

2
y

2
z

we have inside the box, where U = 0,

E=

2 2
n x + n y2 + n z2
2
2m e L

n x , n y , n z = 1, 2 , 3 , .

Outside the box we require = 0.


The minimum energy state inside the box is
P43.35

(a)

n x = n y = n z = 1, with E =

The density of states at energy E is


Hence, the required ratio is

(b)

3 2 2
2m e L2

af
g a8.50 eV f C a8.50f
=
g a7.00 eV f C a7.00f

g E = CE 1 2 .

12
12

= 1.10 .

From Eq. 43.22, the number of occupied states having energy E is

Hence, the required ratio is


At T = 300 K , k BT = 4.14 10 21 J = 0.025 9 eV ,
And

12

a f eb CEg + 1 .
N a8.50 eV f a8.50f L e a
=
M
N a7.00 eV f a7.00f MN e a
N a8.50 eV f a8.50f L
=
N a7.00 eV f a7.00f MN e a
N a8.50 eV f
= 1.55 10
N a7.00 eV f

NE =

E EF k B T

f
f

OP .
+ 1 PQ
OP .
+ 1Q

12

7.00 7 .00 k BT

12

8 .50 7.00 kB T

12
12

2.00

1.50 0 .025 9

25

+1

Comparing this result with that from part (a), we conclude that very few states with E > EF
are occupied.

Chapter 43

Section 43.6
P43.36

559

Electrical Conduction in Metals, Insulators, and Semiconductors


E g = 1.14 eV for Si

(a)

fe

hf = 1.14 eV = 1.14 eV 1.60 10 19 J eV = 1.82 10 19 J so f 2.75 10 14 Hz


c = f ; =

(b)
P43.37

c 3.00 10 8 m s
=
= 1.09 10 6 m = 1.09 m (in the infrared region)
f 2.75 10 14 Hz

Photons of energy greater than 2.42 eV will be absorbed. This means wavelength shorter than

je

6.626 10 34 J s 3.00 10 8 m s
hc
=
= 514 nm .
E
2.42 1.60 10 19 J

All the hydrogen Balmer lines except for the red line at 656 nm will be absorbed.
hc

34

je

J s 3.00 10 8 m s

j J

Eg =

P43.39

If 1.00 10 6 m, then photons of sunlight have energy


E

e6.626 10

P43.38

650 10

e6.626 10
=

hc

max

34

je

J s 3.00 10 8 m s

1.00 10

1.91 eV

j F 1 eV I = 1.24 eV .
GH 1.60 10 J JK
19

Thus, the energy gap for the collector material should be E g 1.24 eV . Since Si has an energy gap
E g 1.14 eV , it will absorb radiation of this energy and greater. Therefore, Si is acceptable as a
material for a solar collector.
P43.40

If the photon energy is 5.5 eV or higher, the diamond window will absorb. Here,

bhf g

max

hc

min

min = 2.26 10
*P43.41

min =

= 5.5 eV :
7

a =

me ke e2
2

je

fe

m = 226 nm .

In the Bohr model we replace k e by


a0 =

6.626 10 34 J s 3.00 10 8 m s
hc
=
5.5 eV
5.5 eV 1.60 10 19 J eV

ke

and m e by m* . Then the radius of the first Bohr orbit,

in hydrogen, changes to

FG IJ
H K

FG
H

FG IJ
H K

IJ b
K

2
me
me
me

a0 =
=
=
11.7 0.052 9 nm = 2.81 nm .
0. 220m e
mke e2
m
me ke e2
m

The energy levels are in hydrogen En =


En =

ke e2 1
and here
2 a0 n 2

F I
GH JK

ke e2 1
ke e2
m En
=
=

2
2a n
me 2
2 m e m a0

For n = 1 , E1 = 0.220

13.6 eV
11.7 2

= 0.021 9 eV .

560

Molecules and Solids

Section 43.7
P43.42

Semiconductor Devices

I = I 0 e ea V f

Thus,

e ea V f

and

V =

k BT
I
ln 1 +
.
e
I0

At T = 300 K ,

V =

k BT

1 .

k BT

IJ
K

FG
H

e1.38 10

=1+

23

I
I0

ja

J K 300 K

1.60 10

19

f lnF 1 + I I = a25.9 mVf lnF 1 + I I .


GH I JK
GH I JK
0

a
f a f
V = a 25.9 mV f lna0.100f =

V = 25.9 mV ln 10.0 = 59.5 mV .

(a)

If I = 9.00 I 0 ,

(b)

If I = 0.900 I 0 ,

59.5 mV .

The basic idea behind a semiconductor device is that a large current or charge can be
controlled by a small control voltage.
P43.43

P43.44

The voltage across the diode is about 0.6 V. The voltage drop across the resistor is
0.025 A 150 = 3.75 V . Thus, 0.6 V 3.8 V = 0 and = 4.4 V .

fa

First, we evaluate I 0 in I = I 0 e ea V f

ja

a f e
e

k BT

1 , given that I = 200 mA when V = 100 mV and T = 300 K .

f
f

1.60 10 19 C 0.100 V
e V
200 mA
I
= 3.86
= 4.28 mA
=
= 3.86 so I 0 = ea V f k T

23
B
k BT
1
1 e
1.38 10
J K 300 K
e
If V = 100 mV ,
I = I 0 e ea V f

*P43.45

(a)

k BT

a f

ja

e V
= 3.86 ; and the current will be
k BT

j a

fe

1 = 4.28 mA e 3.86 1 = 4.19 mA .

The currents to be plotted are

je

I D = 10 6 A e V
IW =

0.025 V

1 ,

20

2.42 V V
745

je

Diode
Wire

10

The two graphs intersect at


V = 0.200 V . The currents
are then

Diode and Wire Currents

I D = 10 6 A e 0. 200 V 0.025 V 1

0.1

V(volts)

= 2.98 mA
FIG. P43.45
2.42 V 0.200 V
= 2.98 mA . They agree to three digits.
IW =
745
I D = I W = 2.98 mA
(b)

V
0.200 V
=
= 67.1
ID
2.98 10 3 A

(c)

d V
dI D
=
dI D
d V

a f LM OP = LM 10 A e
N a f Q N 0.025 V
1

0 . 200 V 0.025 V

OP
Q

= 8.39

0.2

0.3

Chapter 43

Section 43.8
P43.46

(a)
(b)

Superconductivity
See the figure at right.
For a surface current around the outside of the cylinder as shown,
B=

N 0 I

or NI =

a0.540 Tfe2.50 10 mj =
=
e4 10 j T m A
2

10.7 kA .

FIG. P43.46
P43.47

By Faradays law (Equation 32.1),

B
I
B
=L
=A
.
t
t
t

Thus,

A B 0.010 0 m 0.020 0 T
I =
=
= 203 A .
L
3.10 10 8 H

a f b

gb

The direction of the induced current is such as to maintain the B field through the ring.
P43.48

(a)

V = IR
If R = 0 , then V = 0 , even when I 0 .

(b)

The graph shows a direct proportionality.


Slope =

f
f

155 57.8 mA
I
1
=
=
= 43.1 1

R
V
3.61 1.356 mV

R = 0.023 2
(c)

FIG. P43.48

Expulsion of magnetic flux and therefore fewer


current-carrying paths could explain the
decrease in current.

Additional Problems
P43.49

(a)

Since the interatomic potential is the same for both molecules, the spring constant is the
same.
Then f =

1
2

where 12 =

a12 ufa16 uf = 6.86 u and = a14 ufa16 uf = 7.47 u .


14

12 u + 16 u

14 u + 16 u

Therefore,
f14 =

1
2

14

continued on next page

1
2

12

FG IJ = f
H K
12

14

12

12
= 6.42 10 13 Hz
14

6.86 u
= 6.15 10 13 Hz .
7.47 u

561

562

Molecules and Solids

(b)

The equilibrium distance is the same for both molecules.

FG IJ r = FG IJ I
H K
H K
F 7.47 u IJ e1.46 10 kg m j = 1.59 10 kg m
I =G
H 6.86 u K
The molecule can move to the b v = 1, J = 9g state or to the b v = 1, J = 11g state. The energy it
I 14 = 14 r 2 =

14

12

12

14

12

12

46

14

(c)

46

can absorb is either

LMFG 1 + 1 IJ hf
2K
NH
hc LF
1I
= MG 1 + J hf
E =
H
N
2K
E =

or

hc

a f 2 I OP LMFGH 0 12 IJK hf + 10a10 + 1f 2 I OP ,


Q N
Q
OP LMFG 0 + 1 IJ hf + 10a10 + 1f OP .
+ 11a11 + 1f
2 I Q NH
2K
2I Q
2

14 + 9 9 + 1

14

14

14

14

14

14

14

The wavelengths it can absorb are then

=
These are: =

and

P43.50

c
f14 10

b2 I g

or =

14

c
f14 + 11

b2 I g .
14

3.00 10 8 m s

6.15 10 13 Hz 10 1.055 10 34 J s

3.00 10 8 m s

6.15 10 13 Hz + 11 1.055 10 34 J s

2 1.59 10 46 kg m 2

2 1.59 10 46 kg m 2

For the N 2 molecule, k = 2 297 N m, m = 2.32 10 26 kg , r = 1.20 10 10 m , =


k

je

I = r 2 = 1.16 10 26 kg 1.20 10 10 m

= 4.45 10 14 rad s,

= 4.96 m

= 4.79 m .

m
2

= 1.67 10 46 kg m 2 .

For a rotational state sufficient to allow a transition to the first exited vibrational state,
2

2I

a f

a f

J J + 1 = so J J + 1 =

2 I

je

2 1.67 10 46 4.45 10 14
1.055 10

34

j = 1 410 .

Thus J = 37 .

P43.51

FG
H

Emax = 4.5 eV = v +
8.25 > 7.5

P43.52

1
2

IJ
K

a4.5 eVfe1.6 10 J eVj F v + 1 I


G J
e1.055 10 J sje8.28 10 s j H 2 K
19

so

34

14

v=7

With 4 van der Waal bonds per atom pair or 2 electrons per atom, the total energy of the solid is

10 atoms I
jFGH 6.02 4.00
JK =
g

E = 2 1.74 10 23 J atom

23

5. 23 J g .

563

Chapter 43

P43.53

The total potential energy is given by Equation 43.17: U total =

ke e2
B
+ m.
r
r

The total potential energy has its minimum value U 0 at the equilibrium spacing, r = r0 . At this point,
dU
= 0,
dr r = r0
dU
dr

or

P43.54

=
r = r0

F
GH

k e e 2 m 1
r0 .
m

Thus,

B=

Substituting this value of B into U total ,

U 0 =

I
JK

k e2
d
B
e + m
dr
r
r

=
r = r0

kee2
r02

F I
GH JK

mB
= 0.
r0m +1

FG
H

kee2
k e2
k e2
1
1
1
+ e r0m 1 m = e
r0
m
r0
m
r0

IJ
K

1
3
hf + 4. 48 eV = hf + 3.96 eV is the depth
2
2
of the well below the dissociation point. We see hf = 0.520 eV , so the depth of the well is

Suppose it is a harmonic-oscillator potential well. Then,

1
1
hf + 4.48 eV = 0.520 eV + 4.48 eV = 4.74 eV .
2
2
P43.55

(a)

For equilibrium,

dU
= 0:
dx

d
Ax 3 Bx 1 = 3 Ax 4 + Bx 2 = 0
dx

x describes one equilibrium position, but the stable equilibrium position is at


3 Ax 02 = B .
x0 =

(b)

The depth of the well is given by


U0 = U x= x =
0

(c)

3 0.150 eV nm3
3A
=
= 0.350 nm
3.68 eV nm
B

Fx =

U0 = U x= x =
0

a
e

A
B
AB 3 2
BB 1 2

x 03 x 0 3 3 2 A 3 2 3 1 2 A 1 2

3 2

2 3.68 eV nm
2B 3 2
=
32 12
3 A
3 3 2 0.150 eV nm3

12

= 7.02 eV .

dU
= 3 Ax 4 Bx 2
dx

To find the maximum force, we determine finite x m such that

dF
dx

= 0.
x = xm

FG 6 A IJ .
HBK
F B IJ BFG B IJ = B = a3.68 eV nmf
= 3 AG
H 6 A K H 6 A K 12 A 12e0.150 eV nm j
F 1.60 10 J I FG 1 nm IJ = 1.20 10
= 7.52 eV nm G
H 1 eV JK H 10 m K

Thus,

12 Ax 5 + 2Bx 3

Then

Fmax

or

Fmax

x = xm

12

= 0 so that x m =

19

N = 1.20 nN .

564
P43.56

Molecules and Solids

(a)

For equilibrium,

dU
= 0:
dx

d
Ax 3 Bx 1 = 3 Ax 4 + Bx 2 = 0
dx

x describes one equilibrium position, but the stable equilibrium position is at


3 Ax 02 = B or x 0 =

3A
.
B

(b)

The depth of the well is given by U 0 = U x = x =

(c)

Fx =

A
B
AB 3 2
BB 1 2
B3

= 3 2 3 2 1 2 1 2 = 2
.
3
27 A
3 A
x0 x0 3 A

dU
= 3 Ax 4 Bx 2
dx

To find the maximum force, we determine finite x m such that


dFx
dx
P43.57

(a)

= 12 Ax 5 + 2Bx 3
x = xm

x = x0

= 0 then Fmax = 3 A
dU
dr

At equilibrium separation, r = re ,

FG B IJ
H 6AK

FG B IJ =
H 6AK

a r r
a r r
= 2 aB e b e 0 g 1 e b e 0 g = 0 .
r = re

We have neutral equilibrium as re and stable equilibrium at

e abre r0 g = 1 ,

or

re = r0 .

(b)

At r = r0 , U = 0. As r , U B . The depth of the well is B .

(c)

We expand the potential in a Taylor series about the equilibrium point:

af b g

br r g + 12 ddrU br r g
1
U ar f 0 + 0 + a 2BafL ae b g ae b g e e b
MN
2
U r U r0 +

dU
dr

r = r0

2 r r0

r = r0

r r0

This is of the form

(d)

B2
.
12 A

2 r r0

g 1 jO

QP br r g Ba br r g
1
1
kx = k br r g
2
2
0

r = r0

for a simple harmonic oscillator with

k = 2Ba 2 .

Then the molecule vibrates with frequency

f=

The zero-point energy is

ha
1
1
= hf =

2
2

1
2

a
2

2B

B
.
2

B
.
8

Therefore, to dissociate the molecule in its ground state requires energy B

ha

B
.
8

Chapter 43

T=0

P43.58
E
EF
0
0.500
0.600
0.700
0.800
0.900
1.00
1.10
1.20
1.30
1.40
1.50

T = 0.1TF

af

bE E g1 bT T g

e
e
e
e
e
e
e
e0
e +
e +
e +
e +
e +

bE E g1 bT T g

f E

T = 0.2TF

F
e
10 .0
e
e 5.00
e 4.00
e 3.00
e 2.00
e 1.00
e0
e 1.00
e 2.00
e 3 .00
e 4.00
e 5 .00

1.00
1.00
1.00
1.00
1.00
1.00
0.500
0.00
0.00
0.00
0.00
0.00

af

f E

1.000
0.993
0.982
0.953
0.881
0.731
0.500
0.269
0.119
0.047 4
0.018 0
0.006 69

T = 0.5TF

bE E g1 bT T g

F
e
5.00
e
e 2.50
e 2.00
e 1.50
e 1.00
e 0.500
e0
e 0 .500
e 1.00
e 1.50
e 2.00
e 2.50

af

f E

bE E g1 bT T g

F
e
2
.
00
0.993
e
0.924
e 1.00
0.881
e 0.800
0.818
e 0.600
0.731
e 0. 400
0.622
e 0. 200
0.500
e0
0.378
e 0. 200
0.269
e 0. 400
0.182
e 0 .600
0.119
e 0 .800
0.075 9 e 1.00

FIG. P43.58
P43.59

(a)

There are 6 Cl ions at distance r = r0 . The


contribution of these ions to the electrostatic
6 k e e 2
potential energy is
.
r0

There are 12 Na + ions at distance r = 2 r0 .


Their contribution to the electrostatic potential
+12 k e e 2
energy is
. Next, there are 8 Cl ions
2 r0
at distance r = 3 r0 . These contribute a term of
8 k e e 2
3 r0

to the electrostatic potential energy.

FIG. P43.59

To three terms, the electrostatic potential energy is:

FG
H

U = 6 +

12
2

continued on next page

IJ k e
3K r

= 2.13

565

k e2
kee2
with = 2.13 .
or U = e
r0
r0

af

f E

0.881
0.731
0.690
0.646
0.599
0.550
0.500
0.450
0.401
0.354
0.310
0.269

566

Molecules and Solids

(b)

The fourth term consists of 6 Na + at distance r = 2r0 . Thus, to four terms,

U = 2.13 + 3

f k re
e

= 0.866

kee2
.
r0

So we see that the electrostatic potential energy is not even attractive to 4 terms, and that the
infinite series does not converge rapidly when groups of atoms corresponding to nearest
neighbors, next-nearest neighbors, etc. are added together.

ANSWERS TO EVEN PROBLEMS


P43.2

4.3 eV

P43.30

2%

P43.4

(a) 1.28 eV; (b) = 0.272 nm, = 4.65 eV ;


(c) 6.55 nN; (d) 576 N m

P43.32

3.40 10 17 electrons

P43.6

(a) 40.0 eV , 9.66 GHz;


(b) If r is 10% too small, f is 20% too large.

P43.34

see the solution

P43.36

(a) 275 THz; (b) 1.09 m

P43.8

1.46 10 46 kg m 2

P43.38

1.91 eV

P43.10

(a) 1.81 10 45 kg m 2 ; (b) 1.62 cm

P43.40

226 nm

P43.12

(a) 11.8 pm; (b) 7.72 pm; HI is more loosely


bound

P43.42

(a) 59.5 mV; (b) 59.5 mV

P43.44

4.19 mA

P43.46

(a) see the solution; (b) 10.7 kA

P43.48

see the solution

P43.50

37

P43.52

5.23 J g

P43.54

4.74 eV

P43.56

(a) x 0 =

P43.58

see the solution

P43.14

(a) 0, 364 eV , 1.09 meV;


(b) 98.2 meV, 295 meV, 491 meV

P43.16

(a) 472 m ; (b) 473 m ; (c) 0.715 m

P43.18

2.9 10 47 kg m 2

P43.20

only 64.1 THz

P43.22

(a) ~ 10 17 ; (b) ~ 10 5 m 3

P43.24

(a) 0.444 nm, 0.628 nm, 0.769 nm

P43.26

see the solution

P43.28

(a) 1.57 Mm s;
(b) larger by 10 orders of magnitude

B2
3A
B3
; (b) 2
; (c)
B
27 A
12 A