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Chapter 37

Molecules

Conceptual Problems

1 • [SSM] Would you expect NaCl to be polar or nonpolar?

Determine the Concept Yes. Because the center of charge of the positive Na ion

does not coincide with the center of charge for the negative Cl ion, the NaCl

molecule has a permanent dipole moment. Hence, it is a polar molecule.

2 • Would you expect N

2

to be polar or nonpolar?

Determine the Concept Because a N

2

molecule has no permanent dipole

moment, it is a non-polar molecule.

3 • Does neon naturally occur as Ne or Ne

2

? Explain your answer.

Determine the Concept No. Neon naturally occurs 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 atoms of

(a) HF, (b) KBr, (c) N

2

, (d) Ag in solid silver?

Determine the Concept

(a) Because an electron is transferred from the H atom to the F atom, the bonding

mechanism is ionic.

(b) Because an electron is transferred from the K atom to the Br atom, the bonding

mechanism is ionic.

(c) Because the atoms share two electrons, the bonding mechanism is covalent.

(d) Because each valence electron is shared by many atoms, the bonding

mechanism is metallic bonding.

5 •• [SSM] The elements on the far right column of the periodic table are

sometimes called noble gases, both because they are gasses under a wide range of

conditions, and because atoms of these elements almost never react with other

atoms to form molecules or ionic compounds. However, atoms of noble gases

can react if the resulting molecule is formed in an electronic excited state. An

example is ArF. When it is formed in the excited state, it is written ArF* and is

called an excimer (for excited dimer). Refer to Figure 37-13 and discuss how a

Chapter 37

160

diagram for the electronic, vibrational, and rotation energy levels of ArF and

ArF* would look in which the ArF ground state is unstable and the ArF* excited

state is stable. Remark: Excimers are used in certain kinds of lasers.

Determine the Concept The diagram would consist of a non-bonding ground

state with no vibrational or rotational states for ArF (similar to the upper curve in

Figure 37-4) but for ArF* there should be a bonding excited state with a definite

minimum with respect to inter-nuclear separation and several vibrational states as

in the excited state curve of Figure 37-13.

6 • Find other atoms that have the same subshell electron configurations in

their two highest energy orbitals as carbon atoms do. Would you expect the same

type of hybridization for these orbitals as for carbon?

Determine the Concept 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.

7 • How does the value of the effective force constant calculated for a CO

molecule in Example 37-4 compare with the value of the force constant of the

suspension springs on a typical automobile, which is about 1.5 kN/m?

Determine the Concept The effective force constant from Example 37-4 is

1.85×10

3

N/m. This value is about 25% larger than the given value of the force

constant of the suspension springs on a typical automobile.

8 • Explain why the moment of inertia of a diatomic molecule increases

slightly with increasing angular momentum.

Determine the Concept 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.

9 • Why would you expect the separation distance between the two

protons to be larger in a

H

2

+

ion than in a H

2

molecule?

Determine the Concept For H

2

, the concentration of negative charge between the

two protons holds the protons together. In a

+

2

H 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 a

+

2

H ion is not

as effective as the larger charge in a H

2

molecule, and the protons should be

Molecules

161

farther apart. The experimental values support this argument. For H

2

,

r

0

=0.074 nm, while for

+

2

H , r

0

=0.106 nm.

10 • At room temperature an atom typically absorb radiation only from the

ground state, whereas a diatomic molecule typically absorbs radiation from many

different rotational states. Why?

Determine the Concept 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.

11 •• The vibrational energy levels of diatomic molecules are described by a

single vibrational frequency f that is the frequency of vibration of the two atoms

of the molecule along the line through their centers. Would you expect to see one,

or more than one, vibrational frequency in molecules that have three or more

atoms? Consider in particular a water molecule H

2

O (Figure 37-9).

Determine the Concept With more than two atoms in the molecule there will be

more than just one frequency of vibration because there are more possible relative

motions. In advanced mechanics these are known as normal modes of vibration.

Estimation and Approximation

12 •• The potential energy for a diatomic molecule has a minimum as shown

in Figure 37-13. Near this minimum, the graph for the energy as a function of

distance between the atoms may be approximated as a parabola, leading to the

harmonic oscillator model for the vibrating molecule. An improved

approximation is called the anharmonic oscillator and leads to a modification of

the expression for the energy E

ν

= ν +

1

2

( )

hf , where ν =0, 1, 2, …(Equation 37-

18). The modified expression for energy is E

ν

= ν +

1

2

( )

hf − ν +

1

2

( )

2

hf α , where

ν =0, 1, 2, …. For a O

2

molecule, the constants have the values f =4.74 × 10

13

s

–1

and α =7.6 × 10

–3

. Use this formula to estimate the smallest value of the quantum

number ν for which the modified expression differs from the original expression

by 10 percent.

Picture the Problem We can estimate the value of the quantum number ν for

which the improved formula corrects the original formula by 10 percent by setting

the ratio of the correction term to the first term equal to 10 percent and solving for

ν.

Chapter 37

162

Express the ratio of the correction

term to the first term of the

expression for E

ν

and simplify to

obtain:

( )

( )

( )α ν

ν

α ν

2

1

2

1

2

2

1

+ =

+

+

hf

hf

For a correction of 10 percent:

( ) 10 . 0

2

1

= + α ν ⇒

2

1

10

1

− =

α

ν

Substitute numerical values and

evaluate ν :

( )

13 7 . 12

2

1

10 6 . 7 10

1

3

≈ = −

×

=

−

ν

13 •• To understand why quantum mechanics is not needed to describe

many macroscopic systems, estimate the rotational energy quantum number

and

spacing between adjacent energy levels for a baseball (m ∼ 300 g, r ∼ 3 cm)

spinning about its own axis at 20 rev/min. Hint: Pick

so the quantum energy

formula ( ) ( ) I E 2 1

2

**+ = , where =0, 1, 2, ..., (Equation 37-12) gives the
**

correct energy for the given system. Then find the energy increase for the next

highest energy level.

Picture the Problem We can solve Equation 37-12 for and substitute for the

moment of inertia and rotational kinetic energy of the baseball to estimate the

quantum number and spacing between adjacent energy levels for a baseball

spinning about its own axis.

The rotational energy levels are

given by Equation 37-12:

( )

I

E

2

1

2

+

=

where =0, 1, 2, … is the rotational

energy quantum number and I is the

moment of inertia of the ball.

Solving for (+1) yields:

( )

2

2

1

IE

= +

Factoring from the parentheses

gives:

2

2

2 1

1

IE

=

⎟

⎠

⎞

⎜

⎝

⎛

+

The result of our calculation of

will show that >>1. Assuming for

the moment that this is the case:

2

2

2

IE

≈ ⇒

2

2

IE

≈

Because the energy of the ball is

rotational kinetic energy:

2

2

1

rot

ω I K E = =

Molecules

163

Substitute for

E in the expression

for and simplify to obtain:

( ) ( )

ω ω ω

I I I I

= = ≈

2 2 2

2

1

2

The moment of inertia of a ball about

an axis through its diameter is (see

Table 9-1):

2

5

2

mr I =

Substituting for I gives:

5

2

2

ω mr

≈

Substitute numerical values and evaluate :

( )( )

( )

30

34

2

10 2

s J 10 055 . 1 5

s 60

min 1

rev

rad 2

min

rev 20

cm 3 kg 300 . 0 2

× ≈

⋅ ×

⎟

⎟

⎠

⎞

⎜

⎜

⎝

⎛

× ×

≈

−

π

Set =0 to express the spacing

between adjacent energy levels:

2

2 2

r 0

4

5

2 mr I

E

= =

Substitute numerical values and

evaluate E

0r

:

( )

( )( )

J 10 5

cm 0 . 3 g 300 4

s J 10 055 . 1 5

65

2

2

34

r 0

−

−

× ≈

⋅ ×

= E

Remarks: Note that our value for justifies our assumption that >> 1.

14 •• Estimate the quantum number ν and spacing between adjacent energy

levels for a 1.0-kg mass attached to spring. The spring has a force constant equal

to 1200-N/m and the mass-spring system is vibrating with an amplitude of 3.0 cm.

Hint: Pick ν so that the quantum energy formula E

ν

= ν +

1

2

( )

hf , where ν =0, 1,

2, … (Equation 37-18) gives the correct energy for the given system. Then find the

energy increase for the next highest energy level.

Picture the Problem We can solve Equation 37-18 for ν and substitute for the

frequency of the mass-and-spring oscillator to estimate the quantum number ν and

spacing between adjacent energy levels for this system.

The vibrational energy levels are

given by Equation 37-18:

( )hf E

2

1

+ = ν

ν

where ν =0, 1, 2, …

Chapter 37

164

Solve for ν to obtain:

2

1

− =

hf

E

ν

ν

or, because ν >>1,

hf

E

ν

ν ≈

The vibrational energy of the object

attached to the spring is:

2

2

1

kA E =

ν

where A is the amplitude of its motion.

Substitute for E

ν

in the expression for

ν to obtain:

hf

kA

2

2

= ν

The frequency of oscillation f of the

mass-and-spring oscillator is given

by:

m

k

f

π 2

1

=

Substitute for f in the expression for

ν and simplify to obtain:

mk

h

A

k

m

h

kA

2 2

π π

ν = =

Substitute numerical values and evaluate ν :

( )

( )( )

32

34

2

10 1 N/m 1200 kg 0 . 1

s J 10 626 . 6

cm 0 . 3

× ≈

⋅ ×

=

−

π

ν

Set ν =0 in Equation 37-18 to

express the spacing between adjacent

energy levels:

m

k h

hf E

π

ν

4 2

1

0

= =

Substitute numerical values and

evaluate E

0ν

:

J 10 8 . 1

kg 1.0

N/m 1200

4

s J 10 626 . 6

33

34

0

−

−

× =

⋅ ×

=

π

ν

E

Remarks: Note that our value for ν justifies our assumption that ν >> 1.

Molecular Bonding

15 • Calculate the separation of of Na

+

and Cl

–

ions for which the potential

energy of a single ionic unit (one Na

+

ion and one Cl

–

ion) is –1.52 eV.

Molecules

165

Picture the Problem The electrostatic potential energy with U

e

with ions

separated a distance r is given by .

2

r ke U − =

Relate the electrostatic potential

energy of the ions to their separation:

r

ke

U

2

e

− = ⇒

e

2

U

ke

r − =

Substitute numerical values and evaluate r:

( )

( )

nm 0.947

eV

J

10 602 . 1 eV 52 . 1

C 10 602 . 1

C

m N

10 988 . 8

19

2

19

2

2

9

=

⎟

⎠

⎞

⎜

⎝

⎛

× −

×

⎟

⎟

⎠

⎞

⎜

⎜

⎝

⎛ ⋅

×

− =

−

−

r

16 • The equilibrium separation of the atoms in a HF molecule is

0.0917 nm and the measured electric dipole moment of the molecule is

6.40 × 10

–30

C⋅m. What percentage of the HF bond is ionic?

Picture the Problem The percentage of the bonding that is ionic is given by

( ). 100

100 meas

p p

Express the percentage of the

bonding that is ionic:

⎟

⎟

⎠

⎞

⎜

⎜

⎝

⎛

=

100

meas

bonding ionic

100 Percent

p

p

Express the dipole moment for

100% ionic bonding:

er p =

100

Substituting for p

100

gives:

⎟

⎠

⎞

⎜

⎝

⎛

=

er

p

meas

bonding ionic

100 Percent

Substitute numerical values and evaluate the percent ionic bonding:

( )( )

% 6 . 43

nm 0917 . 0 C 10 602 . 1

m C 10 40 . 6

100 Percent

19

30

bonding ionic

=

⎥

⎦

⎤

⎢

⎣

⎡

×

⋅ ×

=

−

−

17 •• The dissociation energy of RbF is 5.12 eV, and the equilibrium

separation of RbF is 0.227 nm. The electron affinity of a fluorine atom is

–3.40 eV and the ionization energy of rubidium is 4.18 eV. Determine the core-

repulsion energy of RbF.

Chapter 37

166

Picture the Problem If we choose the potential energy at infinity to be ΔE, the

total potential energy is U

tot

=U

e

+ΔE +U

rep

, where U

rep

is the energy of

repulsion, which is found by setting the dissociation energy equal to −U

tot

.

Express the total potential energy of

the molecule:

rep e tot

U E U U + Δ + =

The core-repulsive energy is :

( )

d e rep

E U E U + + Δ − = (1)

Calculate the energy ΔE needed to

form Rb

+

and F

−

ions from neutral

rubidium and fluorine atoms:

eV 78 . 0 eV 3.40 eV 18 . 4 = − = ΔE

The electrostatic potential energy

is given by:

r

ke

U

2

e

− =

Substitute numerical values and evaluate U

e

:

( )

( )

eV 34 . 6

eV

J

10 602 . 1 nm 227 . 0

C 10 602 . 1

C

m N

10 988 . 8

19

2

19

2

2

9

e

− =

⎟

⎠

⎞

⎜

⎝

⎛

×

×

⎟

⎟

⎠

⎞

⎜

⎜

⎝

⎛ ⋅

×

− =

−

−

U

Substitute numerical values in

equation (1) and evaluate U

rep

:

( )

eV 44 . 0

eV 12 . 5 eV 34 . 6 eV 78 . 0

rep

=

+ − − = U

18 •• 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. Assume that

the ions are point charges at this separation. (b) The ionization energy of

potassium is 4.34 eV and the electron affinity of chlorine is –3.62 eV. Calculate a

value for the dissociation energy under the assumption that the energy of

repulsion is negligible. (See Figure 37-1) (c) The measured dissociation energy is

4.49 eV. What is the energy due to repulsion of the ions at the equilibrium

separation?

Picture the Problem The potential energy of attraction of the ions is

.

2

e

r ke U − = We can find the dissociation energy from the negative of the sum of

the potential energy of attraction and the difference between the ionization energy

of potassium and the electron affinity of chlorine.

Molecules

167

(a) The potential energy of

attraction of the ions is given by:

r

ke

U

2

e

− =

where ke

2

=1.44 eV⋅nm

Substitute numerical values and

evaluate U

e

:

eV 39 . 5

nm 267 . 0

nm eV 44 . 1

e

− =

⋅

− = U

(b) Express the total potential energy

of the molecule:

rep e tot

U E U U + Δ + =

or, neglecting any energy of repulsion,

E U U Δ + =

e tot

The dissociation energy is the

negative of the total potential

energy:

( ) E U U E Δ + − = − =

e tot calc d,

ΔE is the difference between the

ionization energy of potassium and

the electron affinity of Cl:

eV 0.72 eV 3.62 eV 34 . 4 = − = ΔE

Substitute numerical values and

evaluate E

d,calc

:

( )

eV 67 . 4

eV 72 . 0 eV 39 . 5

calc d,

=

+ − − = E

(c) The energy due to repulsion of

the ions at equilibrium separation is

given by:

meas d, calc d, rep

E E U − =

Substitute numerical values and

evaluate U

rep

:

eV 18 . 0 eV 49 . 4 eV 67 . 4

rep

= − = U

19 •• Indicate an approximate value for the average value of the separation

distance r for two vibrational levels on the potential energy curve for a diatomic

molecule (one of the curves in Figure 37-13). Your teacher claims that the

increase in r

av

with increases in vibration energy explains why solids expand

when heated. Do you agree? If so, give an argument supporting this claim. If not,

give an argument opposing this claim.

Picture the Problem You should agree. The potential energy curve is shown in

the following diagram. The turning points for vibrations of energy E

1

and E

2

are

at the values of r where the energies equal U(r). The average value of r for the

vibrational levels E

1

and E

2

are labeled r

1 av

and r

2 av

. Note that the estimate of r

1 av

is midway between r

1 min

and r

1 max

. The potential is like a special spring that has a

Chapter 37

168

greater spring constant for compressions than it has for extensions. The period of

a spring-and-mass oscillator is inversely proportional to the square root of the

spring constant, so our ″special spring″ spends more time in extension than in

compression. As a result, r

1 av

will be greater than the equilibrium radius.

( ) r U

r 0

2

E

1

E

av 1

r

av 2

r

This argument can be extended to explain why r

2 av

is greater than r

1av

. It is

because the ″spring constant″ for extension, which can be estimated by taking the

average slope of the potential energy curve in the region to the right of the

equilibrium position, is greater for E =E

2

than for E =E

1

. It is also because the

″spring constant″ for compression is greater for E =E

2

than for E =E

1

. It follows

that r

2 av

is greater than r

1 av

. Because r

2,av

is greater than r

1 av

, it follows that as the

vibrational energy of a diatomic molecule increases, the average separation of the

atoms of the molecule increases and, hence, the solid expands with heating.

20 •• Calculate the potential energy of attraction between the Na

+

and Cl

–

ions at the equilibrium separation r

0

=0.236 nm. Compare this result with the

dissociation energy given in Figure 37-1. What is the energy due to repulsion of

the ions at the equilibrium separation?

Picture the Problem We can use

0

2

e

r ke U − = to calculate the potential energy

of attraction between the Na

+

and Cl

−

ions at the equilibrium separation

r

0

=0.236 nm. We can find the energy due to repulsion of the ions at the

equilibrium separation from ( ) E E U U Δ + + − =

d e rep

.

The potential energy of attraction

between the Na

+

and Cl

−

ions at

the equilibrium separation r

0

is

given by:

0

2

e

r

ke

U − =

where ke

2

=1.44 eV⋅nm.

Molecules

169

Substitute numerical values and

evaluate U

e

:

eV 10 . 6

nm 236 . 0

nm eV 44 . 1

e

− =

⋅

− = U

From Figure 37-1:

eV 27 . 4

d

= E

The ratio of the magnitude of the

potential energy of attraction to

the dissociation energy is:

43 . 1

eV 4.27

eV 10 . 6

d

e

= =

E

U

U

rep

is related to U

e

, E

d

, and ΔE

according to:

( ) E E U U Δ + + − =

d e rep

From Figure 37-1:

eV 52 . 1 = ΔE

Substitute numerical values and

evaluate U

rep

:

( )

eV 31 . 0

eV 52 . 1 eV 27 . 4 eV 10 . 6

rep

=

+ + − − = U

21 •• The equilibrium separation of the K

+

and F

–

ions in KF is about

0.217 nm. (a) Calculate the potential energy of attraction of these ions. Assume

that the ions are point charges at this separation. (b) The ionization energy of

potassium is 4.34 eV and the electron affinity of fluorine is –3.40 eV. Find the

dissociation energy by 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.

Picture the Problem The potential energy of attraction of the ions is

.

2

e

r ke U − = We can find the dissociation energy from the negative of the sum of

the potential energy of attraction and the difference between the ionization energy

of potassium and the electron affinity of fluorine.

(a) The potential energy of

attraction between the K

+

and F

−

ions at the equilibrium separation

r

0

is given by:

0

2

e

r

ke

U − =

where ke

2

=1.44 eV⋅nm.

Substitute numerical values and

evaluate U

e

:

eV 64 . 6

nm 217 . 0

nm eV 44 . 1

e

− =

⋅

− = U

Chapter 37

170

(b) Express the total potential energy

of the molecule:

rep e tot

U E U U + Δ + =

or, neglecting any energy of repulsion,

E U U Δ + =

e tot

The dissociation energy is the

negative of the total potential

energy:

( ) E U U E Δ + − = − =

e tot calc d,

ΔE is the difference between the

ionization energy of potassium and

the electron affinity of fluorine:

eV 0.94 eV 3.40 eV 34 . 4 = − = ΔE

Substitute numerical values and

evaluate E

d,calc

:

( )

eV 70 . 5

eV 94 . 0 eV 64 . 6

calc d,

=

+ − − = E

(c) The energy due to repulsion of

the ions at equilibrium separation is

given by:

meas d, calc d, rep

E E U − =

Substitute numerical values and

evaluate U

rep

:

eV 63 . 0 eV 07 . 5 eV 70 . 5

rep

= − = U

Energy Levels of Spectra of Diatomic Molecules

22 • The characteristic rotational energy E

0r

for the rotation of a N

2

molecule is 2.48 × 10

–4

eV. Using this value, find the separation distance of the 2

nitrogen atoms.

Picture the Problem We can relate the characteristic rotational energy E

0r

to the

moment of inertia of the molecule and model the moment of inertia of the N

2

molecule as two point objects separated by a distance r.

The characteristic rotational energy

of a molecule is given by:

I

E

r

2

2

0

=

The moment of inertia of the

molecule is given by:

2

N 2

1

2

N

2

2 r M

r

M I =

⎟

⎠

⎞

⎜

⎝

⎛

=

Substitute for I to obtain:

( )

2

p

2

2

N

2

2

N 2

1

2

0

14 2 r m r M r M

E

r

= = =

Molecules

171

Solving for r gives:

p 0

14

1

m E

r

r

=

Substitute numerical values and evaluate r:

( )

( )( )( )

nm 109 . 0

kg 10 673 . 1 J /eV 10 602 . 1 eV 10 48 . 2 14

1

s J 10 055 . 1

27 19 4

34

=

× × ×

⋅ × =

− − −

−

r

23 • [SSM] The separation of the two oxygen atoms in a molecule of O

2

is actually slightly greater than the 0.100 nm used in Example 37-3. Furthermore,

the characteristic energy of rotation E

0r

for O

2

is 1.78 × 10

–4

eV rather than the

result obtained in that example. Use this value to calculate the separation distance

of the two oxygen atoms.

Picture the Problem We can relate the characteristic rotational energy E

0r

to the

moment of inertia of the molecule and model the moment of inertia of the O

2

molecule as two point objects separated by a distance r.

The characteristic rotational energy

of a molecule is given by:

I

E

r

2

2

0

=

The moment of inertia of the

molecule is given by:

2

O 2

1

2

O

2

2 r M

r

M I =

⎟

⎠

⎞

⎜

⎝

⎛

=

Substitute for I to obtain:

( )

2

p

2

2

O

2

2

O 2

1

2

0

16 2 r m r M r M

E

r

= = =

Solving for r yields:

p 0

1

4 m E

r

r

=

Substitute numerical values and evaluate r:

( )( )( )

nm 121 . 0

kg 10 673 . 1 J /eV 10 602 . 1 eV 10 78 . 1

1

4

s J 10 055 . 1

27 19 4

34

=

× × ×

⎟

⎟

⎠

⎞

⎜

⎜

⎝

⎛ ⋅ ×

=

− − −

−

r

Chapter 37

172

24 •• Show that the reduced mass of a diatomic molecule is always smaller

than the mass of the molecule. Calculate the reduced mass for (a) H

2

, (b) N

2

, (c)

CO, and (d) HCl. Express your answers in unified atomic mass units.

Picture the Problem We can use the definition of the reduced mass to show that

the reduced mass is smaller than either mass in a diatomic molecule.

Express the reduced mass of a two-

body system:

2 1

2 1

m m

m m

+

= μ

Divide the numerator and

denominator of this expression

by m

2

to obtain:

2

1

1

1

m

m

m

+

= μ (1)

Divide the numerator and

denominator of this expression by m

1

to obtain:

1

2

2

1

m

m

m

+

= μ (2)

Because the denominator is greater

than 1 in equations (1) and (2):

1

m < μ and

2

m < μ

(a) For H

2

, m

1

=m

2

=1 u:

( )( )

u 500 . 0

u 1 u 1

u 1 u 1

2

H

=

+

= μ

(b) For N

2

, m

1

=m

2

=14 u:

( )( )

u 00 . 7

u 14 u 14

u 14 u 14

2

N

=

+

= μ

(c) For CO, m

1

=12 u and m

2

=16 u:

( )( )

u 86 . 6

u 16 u 12

u 16 u 12

CO

=

+

= μ

(d) For HCl, m

1

=1 u and

m

2

=35.5 u:

( )( )

u 973 . 0

u 5 . 35 u 1

u 5 . 35 u 1

HCl

=

+

= μ

25 •• A CO molecule has a binding energy of approximately 11 eV. Find the

vibrational quantum number ν that corresponds to 11 eV. (If a CO molecule

actually had this much vibrational energy, it would ″shake″ apart.)

Picture the Problem We can solve Equation 37-18 for ν and substitute for the

frequency of the CO molecule (see Example 37-4) and its binding energy to

estimate the quantum number ν .

Molecules

173

The vibrational energy levels

are given by Equation 37-18:

( )hf E

2

1

+ = ν

ν

⇒

2

1

− =

hf

E

ν

ν

where ν =0, 1, 2, …, k

Substitute numerical values and

evaluate ν :

( )( )

41

2

1

Hz 10 42 . 6 s J 10 626 . 6

eV

J 10 1.602

eV 11

13 34

19

≈

−

× ⋅ ×

×

×

=

−

−

ν

26 •• Derive the equation I = μr

0

2

(Equation 37-14) for the moment of

inertia in terms of the reduced mass of a diatomic molecule.

Picture the Problem 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. We can express the moment of

inertia of a diatomic molecule with respect to its center of mass using the

definitions of the center of mass and the moment of inertia of point particles.

Express the moment of inertia of a

diatomic molecule:

2

2 2

2

1 1

r m r m I + = (1)

The r coordinate of the center of

mass is:

0

2 1

2

CM

r

m m

m

r

+

=

The distances of m

1

and m

2

from the

center of mass are:

CM 1

r r =

and

0

2 1

1

0

2 1

2

0 CM 0 2

r

m m

m

r

m m

m

r r r r

+

=

+

− = − =

Substitute for r

1

and r

2

in equation

(1) to obtain:

2

0

2 1

1

2

2

0

2 1

2

1

⎟

⎟

⎠

⎞

⎜

⎜

⎝

⎛

+

+

⎟

⎟

⎠

⎞

⎜

⎜

⎝

⎛

+

= r

m m

m

m r

m m

m

m I

Simplifying this expression leads

to:

2

0

2 1

2 1

r

m m

m m

I

+

= ⇒

2

0

r I μ = 37-14

where

2 1

2 1

m m

m m

+

= μ

Chapter 37

174

27 •• [SSM] The equilibrium separation between the atoms of a LiH

molecule is 0.16 nm. Determine the energy separation between the =3 and =2

rotational levels of this diatomic molecule.

Picture the Problem We can use the expression for the rotational energy levels

of the diatomic molecule to express the energy separation ΔE between the 3 =

and 2 = rotational levels and model the moment of inertia of the LiH

molecule

as two point objects separated by a distance r

0

.

The energy separation between the

3 = and 2 = rotational levels of

this diatomic molecule is given by:

2 3 = =

− = Δ

E E E

Express the rotational energy levels

E

=3

and E

=2

in terms of E

0r

:

( )

r r

E E E

0 0 3

12 1 3 3 = + =

=

and

( )

r r

E E E

0 0 2

6 1 2 2 = + =

=

Substitute for E

=3

and E

=2

to

obtain:

r r r

E E E E

0 0 0

6 6 12 = − = Δ

The characteristic rotational energy

of a molecule is given by

I

E

r

2

2

0

= .

Hence:

I I

E

2 2

3

2

6

=

⎟

⎟

⎠

⎞

⎜

⎜

⎝

⎛

= Δ

The moment of inertia of the

molecule is given by:

2

0

r I μ =

where μ is the reduced mass of the

molecule.

Substituting for I yields:

( )

2

0 H Li

H Li

2

2

0

H Li

H Li

2

2

0

2

3

3 3

r m m

m m

r

m m

m m

r

E

+

=

+

= = Δ

μ

Substitute numerical values and evaluate ΔE:

( ) ( )

( )( )( ) ( )( )

meV 6 . 5

kg/u 10 661 . 1 J /eV 10 602 . 1 nm 16 . 0 u 1 u 94 . 6

u 1 u 94 . 6 s J 10 055 . 1 3

27 19 2

2

34

=

× ×

+ ⋅ ×

= Δ

− −

−

E

Molecules

175

28 •• The equilibrium separation of the K

+

and Cl

–

ions in KCl is about

0.267 nm. Use this value together with the reduced mass of KCl to calculate the

characteristic rotational energy E

0r

(Equation 37-13) of KCl.

Picture the Problem We can relate the characteristic rotational energy E

0r

to the

moment of inertia of the molecule and model the moment of inertia of the KCl

molecule as two point objects of reduced mass μ separated by a distance r.

The characteristic rotational energy

of a molecule is given by:

I

E

r

2

2

0

=

Express the moment of inertia of

the molecule:

2

0

r I μ =

where

Cl K

Cl K

m m

m m

+

= μ

Substituting for I and simplifying

gives:

( )

2

0 Cl k

Cl K

2

2

0

2

0

2 2 r m m

m m

r

E

r

+

= =

μ

Substitute numerical values and evaluate E

0r

:

( ) ( )

( )( )( ) ( )

meV 0158 . 0

J /eV 10 1.602

1

J 10 53 . 2

kg/u 10 661 . 1 nm 267 . 0 u 35.5 u 1 . 39 2

u 35.5 u 1 . 39 s J 10 055 . 1

19

24

27 2

2

34

0

=

×

× × =

×

+ ⋅ ×

=

−

−

−

−

r

E

29 •• The central frequency for the absorption band of HCl shown in Figure

37-14 is at 8.66 × 10

13

Hz, and the absorption peaks to either side of the central

frequency are separated by about 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 two atoms.

Picture the Problem We can use the expression for the vibrational energies of a

molecule to find the lowest vibrational energy. Because the difference in the

vibrational energy levels depends on both Δf and the moment of inertia I of the

molecule, we can relate these quantities and solve for I. Finally, we can use

2

r I μ = , with μ representing the reduced mass of the molecule, to find the

equilibrium separation of the atoms.

(a) The vibrational energy levels are

given by:

( ) ... , 2 , 1 , 0

2

1

= + = ν ν

ν

hf, E

Chapter 37

176

The lowest vibrational energy

corresponds to ν =0:

hf E

2

1

0

=

Substitute numerical values and evaluate E

0

:

( )( )

eV 179 . 0

J /eV 10 1.602

1

J 10 87 . 2 Hz 10 66 . 8 s J 10 626 . 6

19

20 13 34

2

1

0

=

×

× × = × ⋅ × =

−

− −

E

(b) For Δ =±1:

f h

I

E Δ = = Δ

2

Solving for I and simplifying gives:

f

h

f h

h

f h

I

Δ

=

Δ

=

Δ

=

2 2

2 2

4 4 π π

**Substitute numerical values and
**

evaluate I:

( )

2 47

2 47

11 2

34

m kg 10 3

m kg 10 80 . 2

Hz 10 6 4

s J 10 626 . 6

⋅ × ≈

⋅ × =

×

⋅ ×

=

−

−

−

π

I

(c) The moment of inertia of a HCL

molecule is given by:

2

r I μ =

Replace μ by the reduced mass of a

HCl molecule and r by r

0

to obtain:

2

0

Cl H

Cl H

r

m m

m m

I

+

= ⇒ I

m m

m m

r

Cl H

Cl H

0

+

=

Substitute numerical values and evaluate r

0

:

( )( )

( )

nm 0.1

kg/u 10 661 . 1

m kg 10 80 . 2

u 453 . 34 u 1

u 453 . 34 u 1

27

2 47

0

=

×

⋅ ×

⎥

⎦

⎤

⎢

⎣

⎡ +

=

−

−

r

30 •• Calculate the effective force constant for HCl from its reduced mass

and from the fundamental vibrational frequency obtained from Figure 37-14.

Picture the Problem Let the numeral 1 refer to the H

+

and the numeral 2 to the

Cl

−

ion. For a two-mass and spring system on which no external forces are acting,

the center of mass must remain fixed. We can use this condition to express the net

force acting on either the H

+

or Cl

−

ion. Because this force is a linear restoring

Molecules

177

force, we can conclude that the motion of the object whose mass is m

1

will be

simple harmonic with an angular frequency given by

1 eff

m k = ω .

If the particle whose mass is m

1

moves a distance r

1

from (or toward)

the center of mass, then the particle

whose mass is m

2

must move a

distance:

1

2

1

2

r

m

m

r Δ = Δ from (or toward) the

center of mass.

Express the force exerted by the

spring:

( )

2 1

r r k r k F Δ Δ Δ + − = − =

Substitute for Δr

2

to obtain:

1

2

2 1

1

2

1

1

r

m

m m

k

r

m

m

r k F

Δ

Δ Δ

⎟

⎟

⎠

⎞

⎜

⎜

⎝

⎛ +

− =

⎟

⎟

⎠

⎞

⎜

⎜

⎝

⎛

+ − =

A displacement Δr

1

of m

1

results in a

restoring force:

1 eff 1

2

2 1

r k r

m

m m

k F Δ Δ − =

⎟

⎟

⎠

⎞

⎜

⎜

⎝

⎛ +

− =

where

⎟

⎟

⎠

⎞

⎜

⎜

⎝

⎛ +

=

2

2 1

eff

m

m m

k k

Because this is a linear restoring

force, we know that the motion will

be simple harmonic with the angular

frequency given by:

1

eff

m

k

= ω ⇒

1

eff

2

m

k

f = π

Substitute for k

eff

and simplify to

obtain: ⎟

⎟

⎠

⎞

⎜

⎜

⎝

⎛ +

=

2 1

2 1

2

m m

m m

k f π

or, because

Cl H

Cl H

2 1

2 1

m m

m m

m m

m m

+

=

+

= μ is

the reduced mass of the two-particle

system,

μ

π

k

f = 2

Solving for k yields:

Cl H

Cl H 2 2 2 2

4 4

m m

m m

f f k

+

= = π μ π

Chapter 37

178

Substitute numerical values and evaluate k:

( ) ( )( )( )

( )

N/m 478

u 453 . 35 u 1

kg/u 10 661 . 1 u 453 . 35 u 1 Hz 10 66 . 8 4

27

2

13 2

=

+

× ×

=

−

π

k

31 •• [SSM] The equilibrium separation between the atoms of a CO

molecule is 0.113 nm. For a molecule, such as CO, that has a permanent electric

dipole moment, radiative transitions obeying the selection rule

Δ = ±1 between

two rotational energy levels of the same vibrational level are allowed. (That is, the

selection rule

Δν = ±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 from

= 0 to

= 5 for some vibrational level.

Label the energies in electron volts, starting with E =0 for 0 = . Indicate on your

diagram the transitions that obey

Δ = −1, and calculate the energies of the

photons emitted. (c) Find the wavelength of the photons emitted during each

transition in (b). In what region of the electromagnetic spectrum are these

photons?

Picture the Problem We can find the reduced mass of CO and the moment of

inertia of a CO molecule from their definitions. The energy level diagram for the

rotational levels from 0 = to 5 = can be found using . 2

0 1 , r

E E

= Δ

−

Finally,

we can find the wavelength of the photons emitted for each transition using

r

E

hc

E

hc

0 1 ,

1 ,

2 Δ

=

Δ

=

−

−

λ .

(a) Express the moment of inertia

of CO:

2

0

r I μ =

where μ is the reduced mass of the CO

molecule.

The reduced mass of the CO molecule

is given by:

O C

O C

m m

m m

+

= μ

Substituting for μ gives:

O C

2

0 O C

m m

r m m

I

+

=

Molecules

179

Substitute numerical values (r

0

=0.113 nm) and evaluate I:

( )( )

( )( )

2 46

2 46 2 27

m kg 10 45 . 1

m kg 10 454 . 1 nm 113 . 0 kg/u 10 661 . 1

u 16 u 12

u 16 u 12

⋅ × =

⋅ × = ×

⎟

⎟

⎠

⎞

⎜

⎜

⎝

⎛

+

=

−

− −

I

The characteristic rotational energy

E

0r

is given by:

I

E

r

2

2

0

=

Substitute numerical values and evaluate E

0r

:

( ) ( )

( )

meV 0.239 meV 0.2385

m kg 10 454 . 1 2

J /eV 10 602 . 1 s eV 10 58 . 6

2 46

19

2

16

0

= =

⋅ ×

× ⋅ ×

=

−

− −

r

E

(b) The energy level diagram is

shown to the right. Note that ΔE

,

−1

,

the energy difference between

adjacent levels for Δ =−1, is

. 2

0 1 , r

E E

= Δ

−

meV 76 . 4 , 4 = = E l

meV 86 . 2 , 3 = = E l

meV 43 . 1 , 2 = = E l

meV 476 . 0 , 1 = = E l

0 , 0 = = E l

meV 14 . 7 , 5 = = E l

Chapter 37

180

The energies of the photons emitted

in each transition are given by

1 , −

Δ

E . Hence:

meV 38 . 2

meV 76 . 4 meV 14 . 7

4 , 5

=

− = ΔE

meV .90 1

meV 86 . 2 meV 76 . 4

3 , 4

=

− = ΔE

meV .43 1

meV 43 . 1 meV 86 . 2

2 , 3

=

− = ΔE

meV .25 1

meV 476 . 0 meV 43 . 1

1 , 2

=

− = ΔE

meV 476 . 0

0 meV 476 . 0

0 , 1

=

− = ΔE

(c) Express the energy difference

1 . −

Δ

E between energy levels in

terms of the frequency of the emitted

radiation:

1 , 1 , − −

= Δ

hf E

Because :

1 , 1 , − −

=

λ f c

r

E

hc

E

hc

0 1 ,

1 ,

2 Δ

=

Δ

=

−

−

λ

Substitute numerical values to obtain:

( )( )

( )

m 2600

meV 2385 . 0 2

m/s 10 998 . 2 s eV 10 136 . 4

8 15

1 ,

μ

λ =

× ⋅ ×

=

−

−

For =1:

m 2600

1

m 2600

0 , 1

μ

μ

λ = =

For =2:

m 1300

2

m 2600

1 , 2

μ

μ

λ = =

For =3:

m 867

3

m 2600

2 , 3

μ

μ

λ = =

For =4:

m 650

4

m 2600

3 , 4

μ

μ

λ = =

Molecules

181

For =5:

m 520

5

m 2600

4 , 5

μ

μ

λ = =

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

32 •• Two objects, one of mass m

1

and the other of mass m

2

, are connected

to opposite ends of a spring of force constant k

F

. The objects are released from

rest with the spring compressed. (a) Show that when the spring is extended and

the object of mass m

1

is a distance Δr

1

from its equilibrium position in the center-

of-mass reference frame, the force exerted by the spring is given by

( )

1 1 F

r m k F Δ − = μ , where μ is the reduced mass. (b) Show that the frequency of

oscillation f is related to k and μ by μ π

F

2 k f = .

Picture the Problem For a two-mass and spring system on which no external

forces are acting, the center of mass must remain fixed. We can use this condition

to express the net force acting on either object. Because this force is a linear

restoring force, we can conclude that the motion of the object whose mass is m

1

will be simple harmonic with an angular frequency given by

1 eff

m k = ω .

Substitution for k

eff

will lead us to the result given in (b).

(a) If the particle whose mass is m

1

moves a distance Δr

1

from (or

toward) the center of mass, then the

particle whose mass is m

2

must

move a distance:

1

2

1

2

r

m

m

r Δ = Δ from (or toward) the

center of mass.

Express the force exerted by the

spring:

( )

2 1 F F

r r k r k F Δ + Δ − = Δ − =

Substitute for Δr

2

and simplify to

obtain:

1

1

F 1

2 1

2 1

1

F

1

2

2 1

F

1

2

1

1 F

r

m

k r

m m

m m

m

k

r

m

m m

k

r

m

m

r k F

Δ

⎟

⎟

⎠

⎞

⎜

⎜

⎝

⎛

− = Δ

⎟

⎟

⎟

⎟

⎠

⎞

⎜

⎜

⎜

⎜

⎝

⎛

+

− =

Δ

⎟

⎟

⎠

⎞

⎜

⎜

⎝

⎛ +

− =

⎟

⎟

⎠

⎞

⎜

⎜

⎝

⎛

Δ + Δ − =

μ

where

2 1

2 1

m m

m m

+

= μ is the reduced mass

of the spring and mass oscillator.

Chapter 37

182

(b) A displacement Δr

1

of m

1

results

in a restoring force given by:

1 eff 1

2

2 1

F

r k r

m

m m

k F Δ − = Δ

⎟

⎟

⎠

⎞

⎜

⎜

⎝

⎛ +

− =

where

⎟

⎟

⎠

⎞

⎜

⎜

⎝

⎛ +

=

2

2 1

F eff

m

m m

k k

Because this is a linear restoring

force, we know that the motion will

be simple harmonic with an angular

frequency given by:

1

eff

m

k

= ω ⇒

1

eff

2

1

2 m

k

f

π π

ω

= =

Substitute for k

eff

and simplify to

obtain: ⎟

⎟

⎠

⎞

⎜

⎜

⎝

⎛ +

= =

2 1

2 1

F

2

1

2 m m

m m

k f

π π

ω

or, because

2 1

2 1

m m

m m

+

= μ is the reduced

mass of the two-particle system,

μ

π

F

2

k

f = .

33 ••• Calculate the reduced masses for H

35

Cl and H

37

Cl molecules and the

fractional difference Δμ/μ. Show that the mixture of isotopes in HCl leads to a

fractional difference in the frequency of a transition from one rotational state to

another given by Δf/f =–Δμ/μ. Compute Δf/f and compare your result with Figure

37-17.

Picture the Problem We can use the definition of the reduced mass to find the

reduced mass for the H

35

Cl and H

37

Cl molecules and the fractional difference

μ μ Δ . Because the rotational frequency is proportional to 1/I, where I is the

moment of inertia of the system, and I is proportional to μ, we can obtain an

expression for f as a function of μ that we differentiate implicitly to show that

μ μ Δ − = Δ f f .

For H

35

Cl:

( )( )

u 972 . 0 u

36

35

u 1 u 35

u 1 u 35

Cl H

35

= =

+

= μ

For H

37

Cl:

( )( )

u 974 . 0 u

38

37

u 1 u 37

u 1 u 37

Cl H

37

= =

+

= μ

Molecules

183

The fractional difference is:

( )( )

00150 . 0

u

38 36 2

37 36 38 35

u

38 36

38 35 37 36

u

38

37

u

36

35

2

1

u

36

35

u

38

37

=

× + ×

×

× − ×

=

⎟

⎠

⎞

⎜

⎝

⎛

+

−

=

Δ

μ

μ

The rotational frequency is

proportional to I

−1

, where I is the

moment of inertia of the system.

Because I is proportional to μ:

μ

C

f =

and

μ μ d C df

2 −

− =

Divide df by f to obtain:

μ

μ d

f

df

− = and

μ

μ Δ

− ≈

Δ

f

f

From Figure 37-17: Hz 10 1 Hz 10 01 . 0

11 13

× = × ≈ Δf

For f =8.40×10

13

Hz:

001 . 0

Hz 10 40 . 8

Hz 10 1

13

11

=

×

×

≈

Δ

f

f

This result is in fair agreement (about 20% difference) with the calculated result.

Note that Δf is difficult to determine precisely from Figure 37-17.

General Problems

34 • Show that when one atom of a diatomic molecule is much more

massive than the other the reduced mass is approximately equal to the mass of the

lighter atom.

Picture the Problem We can use the definition of the reduced mass to 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.

Express the reduced mass of a two-

body system:

2 1

2 1

m m

m m

+

= μ

Divide the numerator and

denominator of this expression by m

2

to obtain:

2

1

1

1

m

m

m

+

= μ

Chapter 37

184

If m

2

>>m

1

, then:

1

2

1

<<

m

m

and

1

m ≈ μ

35 •• The equilibrium separation between the nuclei of a CO molecule is

0.113 nm. Determine the energy difference between the

= 2 and

= 1 rotational

energy levels of this molecule.

Picture the Problem The rotational energy levels are given by

( )

. ... , 2 , 1 , 0 ,

2

1

2

=

+

=

I

E

Express the energy difference

between these rotational energy

levels:

1 2 2 , 1

E E E − = Δ

Express E

2

and E

1

:

( )

I I

E

2 2

2

3

2

1 2 2

=

+

=

and

( )

I I

E

2 2

1

2

1 1 1

=

+

=

Substitute to obtain:

I I I

E

2 2 2

2 , 1

2 3

= − = Δ

The moment of inertia of the

molecule is given by:

2

0

r I μ =

where μ is the reduced mass of the

molecule.

Substituting for I yields:

( )

2

0 O C

O C

2

2

0

O C

O C

2

2

0

2

2 , 1

2

2 2

r m m

m m

r

m m

m m

r

E

+

=

+

= = Δ

μ

Substitute numerical values and evaluate ΔE

1,2

:

( ) ( )

( )( )( ) ( )( )

meV 955 . 0

J /eV 10 1.602 kg/u 10 661 . 1 nm 113 . 0 u 12 u 16

u 16 u 12 s J 10 055 . 1 2

19 27 2

2

34

2 , 1

=

× ×

+ ⋅ ×

= Δ

− −

−

E

Molecules

185

36 •• The effective force constant for a HF molecule is 970 N/m. Find the

frequency of vibration for this molecule.

Picture the Problem We can use the result of Problem 32 to find the frequency

of vibration of the HF molecule.

In Problem 32 it was established

that:

μ π

k

f

2

1

= where μ is the reduced

mass of the HF molecule.

The reduced mass of the HF

molecule is given by:

F H

F H

m m

m m

+

= μ

Substitute for μ and simplify to

obtain:

( )

F H

F H

F H

F H

2

1

2

1

m m

m m k

m m

m m

k

f

+

=

+

=

π π

Substitute numerical values and evaluate f:

( )( )

( )( )( )

Hz 10 25 . 1

kg/u 10 661 . 1 u 19 u 1

u 19 u 1 N/m 970

2

1

14

27

× =

×

+

=

−

π

f

37 •• The frequency of vibration of a NO molecule is 5.63 × 10

13

Hz. Find

the effective force constant for NO.

Picture the Problem We can use the result of Problem 32 to find the effective

force constant for NO.

In Problem 32 it was established

that:

μ π

k

f

2

1

= ⇒ μ π

2 2

4 f k = where μ is

the reduced mass of a NO molecule.

The reduced mass of the NO

molecule is given by:

O N

O N

m m

m m

+

= μ

Substituting for μ gives:

O N

O N

2 2

4

m m

m m f

k

+

=

π

Chapter 37

186

Substitute numerical values and evaluate k:

( ) ( )( )( )

kN/m 55 . 1

u 16 u 14

kg/u 10 661 . 1 u 16 u 14 s 10 63 . 5 4

27

2

1 13 2

=

+

× ×

=

− −

π

k

38 •• The effective force constant of the hydrogen bond in a H

2

molecule is

580 N/m. Obtain the energies of the four lowest vibrational levels of the H

2

, HD,

and D

2

molecules, where H is protium and D is deuterium, and find the

wavelengths of photons resulting from transitions between adjacent vibrational

levels for each of these molecules.

Picture the Problem We can use the expression for the vibrational energy levels

of a molecule and the expression for the frequency of oscillation from Problem 32

to find the four lowest vibrational levels of the given molecules.

The vibrational energy levels are

given by:

( ) ... , 2 , 1 , 0 where

2

1

= + = ν ν

ν

hf, E

In Problem 32 we showed that the

frequency of oscillation is:

μ π

k

f

2

1

= where

2 1

2 1

m m

m m

+

= μ

Substitute for f and μ to obtain:

( ) ( )

( ) ( )

2 1

2 1 2

1

2 1

2 1 2

1

2

2

m m

m m

k

h

m m

k m m h

E

+ +

=

+ +

=

π

ν

π

ν

ν

Substitute numerical values to obtain:

( )( ) ( )

( )( )

( )

2 1

2 1

2

1

2 1

2 1

27

15

2

1

u eV 389 . 0

kg/u 10 661 . 1

N/m 580

2

s eV 10 136 . 4

m m

m m

m m

m m

E

+

⋅ + =

+

×

⋅ × +

=

−

−

ν

π

ν

ν

Substitute for m

1

and m

2

and evaluate E

0

for H

2

:

( )

( )

( )( )

eV 275 . 0

u 1 u 1

u 1 u 1

u eV 389 . 0

2

1

0

=

+

⋅ = E

Molecules

187

Proceed similarly to complete the

table to the right:

H

2

HD D

2

(eV) (eV) (eV)

0

275 . 0 238 . 0 195 . 0

1

825 . 0 715 . 0 584 . 0

2

375 . 1 191 . 1 973 . 0

3

925 . 1 667 . 1 362 . 1

The energies of the photons resulting

from transitions between adjacent

vibrational levels of these molecules

are given by:

λ

hc

hf E = = Δ ⇒

E

hc

Δ

= λ

Evaluate λ(H

2

):

( ) m 25 . 2

eV 550 . 0

nm eV 1240

H

2

μ λ =

⋅

=

Evaluate λ(HD):

( ) m 60 . 2

eV 477 . 0

nm eV 1240

HD μ λ =

⋅

=

Evaluate λ(D

2

):

( ) m 19 . 3

eV 389 . 0

nm eV 1240

D

2

μ λ =

⋅

=

39 •• The potential energy between two atoms in a molecule separated

by a distance r can often be described rather well by the Lenard–J ones (or 6-12)

potential function, which can be written as

U = U

0

a

r

⎛

⎝

⎜

⎞

⎠

⎟

12

− 2

a

r

⎛

⎝

⎜

⎞

⎠

⎟

6

⎡

⎣

⎢

⎢

⎤

⎦

⎥

⎥

where U

0

and a are constants. Find the equilibrium separation r

0

in terms of a.

Hint: At the equilibrium separation the potential energy is a minimum. Find U

min

,

the value of U when r =r

0

. Use Figure 37-4 to obtain numerical values of r

0

and

U

0

for a H

2

molecule, and express your answers in nanometers and electron volts.

Picture the Problem We can set the derivative of the potential energy function

equal to zero to find the value of r for which it is either a maximum or a

minimum. Examination of the second derivative of this function at the value for r

obtained from setting the first derivative equal to zero will establish whether the

function is a relative maximum or relative minimum at this point.

Chapter 37

188

Differentiate the potential energy

function with respect to r:

⎥

⎥

⎦

⎤

⎢

⎢

⎣

⎡

⎟

⎠

⎞

⎜

⎝

⎛

−

⎟

⎠

⎞

⎜

⎝

⎛

− =

⎪

⎭

⎪

⎬

⎫

⎪

⎩

⎪

⎨

⎧

⎥

⎥

⎦

⎤

⎢

⎢

⎣

⎡

⎟

⎠

⎞

⎜

⎝

⎛

−

⎟

⎠

⎞

⎜

⎝

⎛

=

5 11

0

6 12

0

12 12

2

r

a

r

a

r

U

r

a

r

a

U

dr

d

dr

dU

Set the derivative equal to zero for

extrema:

0 12 12

5

0

11

0 0

0

=

⎥

⎥

⎦

⎤

⎢

⎢

⎣

⎡

⎟

⎟

⎠

⎞

⎜

⎜

⎝

⎛

−

⎟

⎟

⎠

⎞

⎜

⎜

⎝

⎛

− =

r

a

r

a

r

U

dr

dU

Solve for r

0

to obtain a candidate

for r that minimizes the Lenard-

J ones potential:

a r =

0

To show that r

0

=a corresponds to a

minimum, differentiate U a second

time to obtain:

⎥

⎥

⎦

⎤

⎢

⎢

⎣

⎡

⎟

⎠

⎞

⎜

⎝

⎛

−

⎟

⎠

⎞

⎜

⎝

⎛

=

⎪

⎭

⎪

⎬

⎫

⎪

⎩

⎪

⎨

⎧

⎥

⎥

⎦

⎤

⎢

⎢

⎣

⎡

⎟

⎠

⎞

⎜

⎝

⎛

−

⎟

⎠

⎞

⎜

⎝

⎛

− =

4 10

2

0

5 11

0

2

2

60 132

12 12

r

a

r

a

r

U

r

a

r

a

r

U

dr

d

dr

U d

Evaluate this second derivative of

the potential at r

0

=a:

[ ] 0

72

60 132

2

0

2

0

2

2

> = − =

=

a

U

a

U

dr

U d

a r

Therefore, we can conclude that

a r =

0

minimizes the potential function.

Evaluate

min

U :

( )

0

6 12

0 min

2

U

a

a

a

a

U a U U

− =

⎥

⎥

⎦

⎤

⎢

⎢

⎣

⎡

⎟

⎠

⎞

⎜

⎝

⎛

−

⎟

⎠

⎞

⎜

⎝

⎛

= =

From Figure 37-4:

nm 074 . 0

0

= r

and

eV 52 . 4

0

= U

40 •• In this problem, you are to determine how the van der Waals force

between a polar molecule and a nonpolar molecule depends on the distance

between the molecules. Let the polar molecule be at the origin and let its dipole

moment be in the +x direction. In addition, let the nonpolar molecule be on the x

axis a distance x away. (a) How does the electric field strength due to an electric

Molecules

189

dipole vary with the distance from the dipole in a given direction? (b) Use (1) that

the potential energy U of an electric dipole of dipole moment

p in an electric

field

E can be expressed as

U = −

p ⋅

**E , and (2) that the induced dipole moment
**

' p

of the nonpolar molecule is in the direction of

**E , and that p′ is proportional to
**

E, to determine how the potential energy of interaction of the two molecules

depends on the separation distance x. (c) Using F

x

= −dU/ dx , determine how the

force between the two molecules depends on distance.

Picture the Problem We can use Equation 21-10 to establish the dependence of

E on x and the dependence of an induced dipole on the field that induces it to

establish the dependence of p and U on x.

(a) In terms of the dipole moment,

the electric field on the axis of the

dipole at a point a great distance x

away has the magnitude (see

Equation 21-10):

3

2

x

kp

E = ⇒

3

1

x

E ∝

(b) Because the induced dipole

moment is proportional to the field

that induces it:

3

1

x

p ∝ and

6

1

x

U ∝ ⋅ − = E p

**(c) Differentiate U with respect to x
**

to obtain:

7

1

x dx

dU

F

x

∝ − =

41 •• Find the dependence of the force on the separation distance between

the two polar molecules described in Problem 40.

Picture the Problem For the case of two polar molecules, p does not depend on

the field E. The dependence of F on the separation distance x can be found from

dU/dx.

Because p does not depend on the

electric field in which the polar

molecules find themselves:

3

1

x

U ∝

Differentiate U with respect to x to

obtain:

4

1

x dx

dU

F

x

∝ − =

Chapter 37

190

42 •• Use the infrared absorption spectrum of HCl in Figure 37-17 to obtain

(a) the characteristic rotational energy E

0r

(in eV) and (b) find vibrational

frequency f and the vibrational energy hf (in eV).

Picture the Problem (a) Except for a gap of 4E

0r

/h at the vibrational frequency f,

the absorption spectrum contains frequencies equally spaced at 2E

0r

/h. We can

measure this spacing of the absorption peaks to obtain E

0r

. (b) We can use the

expression for the vibrational and rotational energies of a molecule, in

conjunction with Figure 37-17 to find f and hf.

(a) Letting Δf represent the

frequency gap, we have:

h

E

f

r 0

2

= Δ ⇒ f h E

r

Δ =

2

1

0

Estimating from Figure 37-17, the

frequency gap is approximately:

Hz 10 0 . 7

11

× = Δf

where the peaks at 8.40 × 10

13

Hz and

8.61 × 10

13

Hz were used.

Substitute numerical values and evaluate E

0r

:

( )( ) meV 4 . 1 Hz 10 0 . 7 s eV 10 136 . 4

11 15

2

1

0

= × ⋅ × =

−

r

E

(b) The vibrational energy levels are

given by:

( ) ... , 2 , 1 , 0

2

1

= + = ν ν

ν

hf, E

The lowest vibrational energy

corresponds to ν =0:

hf E

2

1

0

= ⇒

0

2E hf = (1)

Determine f from Figure 37-17:

Hz 10 66 . 8

13

× = f

Substitute for f and h and evaluate E

0

:

( )( ) eV 179 . 0 Hz 10 66 . 8 s eV 10 136 . 4

13 15

2

1

0

= × ⋅ × =

−

E

Substitute in equation (1) and

evaluate hf:

( ) eV 358 . 0 eV 179 . 0 2 = = hf

43 • 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 NaCl in kcal/mol.

Molecules

191

Picture the Problem We can use conversion factors to convert eV/molecule into

kcal/mol.

(a)

kcal/mol 0 . 23

eV

J 10 602 . 1

mole

molecules 10 022 . 6

J 4184

kcal 1

molecule

eV

1

molecule

eV

1

19 23

=

×

×

×

× × =

−

(b) The dissociation energy of NaCl,

in eV/molecule, is 4.27 eV/molecule.

Using the conversion factor in (a),

express this energy in kcal/mol:

kcal/mol 2 . 98

mol

kcal 0 . 23

molecule

eV 27 . 4

= ×

Chapter 37

192

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