Chapter 8

Chapter 8 Problem Solutions
1. The energy needed to detach the electron from a hydrogen atom is 13.6 eV, but the energy
needed to detach an electron from a hydrogen molecule is 15.7 eV. Why do you think the latter
energy is greater?
【sol】
The nuclear charge of +2e is concentrated at the nucleus, while the electron charges' densities
are spread out in (presumably) the 1s subshell. This means that the additional attractive force
of the two protons exceeds the mutual repulsion of the electrons to increase the binding energy.
3. At what temperature would the average kinetic energy of the molecules in a hydrogen sample
be equal to their binding energy?
【sol】
Using 4.5 eV for the binding energy of hydrogen,
3 2 4.5 eV
kT = 4.5 eV or T = = 3.5 × 104 K
2 3 8.62 × 10 eV/K
-5
Inha University Department of Physics

5. When a molecule rotates, inertia causes its bonds to stretch. (This is why the earth bulges at
the equator.) What effects does this stretching have on the rotational spectrum of the molecule?
【sol】
The increase in bond lengths in the molecule increases its moment of inertia and accordingly
decreases the frequencies in its rotational spectrum (see Equation (8.9)). In addition, the higher the
quantum number J (and hence the greater the angular momentum), the faster the rotation and the
greater the distortion, so the spectral lines are no longer evenly spaced.
Quantitatively, the parameter I (the moment of inertia of the molecule) is a function of J, with I
larger for higher J. Thus, all of the levels as given by Equation (8.11) are different, so that the
spectral lines are not evenly spaced. (It should be noted that if I depends on J, the algebraic steps
that lead to Equation (8.11) will not be valid.)
7. The J=0àJ=1 rotational absorption line occurs at 1.153x1011 Hz in 12C16O and at 1.102x10 11
Hz in ?C16O. Find the mass number of the unknown carbon isotope.
【sol】
From Equation (8.11), the ratios of the frequencies will be the ratio of the moments of inertia. For
the different isotopes, the atomic separation, which depends on the charges of the atoms, will be
essentially the same. The ratio of the moments of inertia will then be the ratio of the reduced masses.
Denoting the unknown mass number by x and the ratio of the frequencies as r, r in terms of x is

x ⋅ 16
r = x + 16
12 ⋅ 16
12 + 16
Solving for x in terms of r,
48r
x=
7 − 3r
Using r = (1.153)/(1.102) in the above expression gives x = 13.007, or the integer 13 to three
significant figures.
9. The rotational spectrum of HCI contains the following wavelengths:

12.03 x 10-5 m, 9.60 x 10-5 m, 8.04 x 10-5 m, 6.89 x 10-5 m, 6.04 x 10-5 m
If the isotopes involved are 1H and 35Cl, find the distance between the hydrogen and
chlorine nuclei in an HCl molecule.

【sol】
The corresponding frequencies are, from ν = c/λ , and keeping an extra significant figure,
in multiplies of 1012 Hz:
2.484, 3.113, 4.337, 4.947
The average spacing of these frequencies is ∆v = 0.616 x 1012 Hz. (A least-squares fit from a
spreadsheet program gives 0.6151 if c = 2.998 x 108 m/s is used.) From Equation (8.11), the
spacing of the frequencies should be ∆v = /2πI ; Solving for I and using ∆v as found above,
h 1.055 × 10−34 J ⋅ s − 47
I = = = 2 . 73 × 10 kg ⋅ m 2
2π∆ν 2π ( 0.6151 × 1012 Hz )
The reduced mass of the HCI molecule is (35/36)rnH, and so the distance between the nuclei is
I 36 × ( 2.73 × 10−47 kg ⋅ m 2 )
R= = − 27
= 0.129 nm
µ 35 × (1.67 × 10 kg)
(keeping extra significant figures in the intermediate calculation gives a result that is
rounded to 0.130 nm to three significant figures).

11. A 200Hg35Cl Molecule emits a 4.4-cm photon when it undergoes a rotational transition
from j = 1 to j = 0. Find the interatomic distance in this molecule.
【sol】
Using ν1→0 = c/λ and I = m’ R2 in Equation (8.11) and solving for R,
hλ
R2 =
2πm ′c
For this atom, m’ = mH(200x35)/(200 + 35), and
(1.055 × 10− 34 J ⋅ s)(4.4 × 10− 2 m)
R= −27
= 0.223 nm
2π (1.67 × 10 kg)(3.0 × 10 m/s)8
or 0.22 nm to two significant figures.

13. In Sec. 4.6 it was shown that, for large quantum numbers, the frequency of the radiation
from a hydrogen atom that drops from an initial state of quantum number n to a final state of
quantum number n - 1 is equal to the classical frequency of revolution of an electron in the
n-th Bohr orbit. This is an example of Bohr's correspondence principle. Show that a similar
correspondence holds for a diatomic molecule rotating about its center of mass.
【sol】
Equation (8.11) may be re-expressed in terms of the frequency of the emitted photon when
the molecule drops from the J rotational level to the J - 1 rotational level,
hJ
ν J →J −1 = .
2πI
For large J, the angular momentum of the molecule in its initial state is
L = h J ( J + 1) = hJ 1 + 1/ J ≈ hJ
Thus, for large J,
L
ν ≈ , or L = ωI ,
2πI
the classical expression.

15. The hydrogen isotope deuterium has an atomic mass approximately twice that of
ordinary hydrogen. Does H2 or HD have the greater zero-point energy? How does this
affect the binding energies of the two molecules?
【sol】
The shape of the curve in Figure 8.18 will be the same for either isotope; that is, the
value of k in Equation (8.14) will be the same. HD has the greater reduced mass, and
hence the smaller frequency of vibration vo and the smaller zero- point energy. HD is the
more tightly bound, and has the greater binding energy since its zero-point energy
contributes less energy to the splitting of the molecule.
17. The force constant of the 1H19F molecule is approximately 966 N/m. (a) Find the
frequency of vibration of the molecule. (b) The bond length in 1H19F is approximately 0.92
nm. Plot the potential energy of this molecule versus internuclear distance in the vicinity
of 0.92 nm and show the vibrational energy levels as in Fig. 8.20.
【sol】
(a) Using m'= (19/20)mH in Equation (8.15),
1 966 N/m 20
νo = = 1.24 × 1014 Hz
2π 1.67 × 10 kg 19
- 27

k
(b) Eo = 12 h = 4.11 X 10-20 J. The levels are shown below, where the vertical
m′
scale is in units of 10-20 J and the horizontal scale is in units of 10-11 m.
19. The lowest vibrational states of the 23Na35Cl molecule are 0.063 eV apart. Find the
approximate force constant of this molecule.
【sol】
From Equation (8.16), the lower energy levels are separated by ∆E = hvo, and vo = ∆E /h.
Solving Equation (8.15) for k,
 ∆E 
k = m ′( 2πνo )2 = m ′ 
 h 

Using m’ = mH (23·35)/(23 + 35),
23 ⋅ 35 − 27  (0.063 eV)(1.60 × 10-19 J/eV) 
k= (1.67 × 10 kg)  = 213 N/m
58 4.14 × 10 eV ⋅ s
-15 
 
or 2.1 x102 N/m to the given two significant figures.
21. The bond between the hydrogen and chlorine atoms in a 1H35Cl molecule has a force
constant of 516 N/m. Is it likely that an HCl molecule will be vibrating in its first excited
vibrational state at room temperature? Atomic masses are given in the Appendix.
【sol】 Using
k 35
∆E = hνo = h and m ′ = mH ,
m′ 36
516 N/m 36
∆ E = (1.055 × 10−34 J ⋅ s) − 27
= 5 . 94 × 10 − 20
J = 0.371 eV
1.67 × 10 kg 35
At room temperature of about 300 K,
k T = (8.617 x 10-5 eV/K) (300 K) = 0.026 eV.
An individual atom is not likely to he vibrating in its first ex cited level, but in a
large collection of atoms, it is likely that some of these atoms will be in the first excited state.
It's important to note that in the above calculations, the symbol "k" has been used for both a
spring constant and Boltzmann's constant, quantities that are not interchangeable.

Chapter 8

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Chapter 8

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Chapter 8 Problem Solutions

Inha University Department of Physics

Inha University Department of Physics

9. The rotational spectrum of HCI contains the following wavelengths:

Inha University Department of Physics

Inha University Department of Physics

or 0.22 nm to two significant figures.

Inha University Department of Physics

Inha University Department of Physics

Inha University Department of Physics

Inha University Department of Physics

Inha University Department of Physics

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