University of Minnesota

Statistical Molecular Thermodynamics

Homework Week 1
1. The diagram below shows the energy of a diatomic molecule as a function of the
separation between the atoms, R.

electronic excited state

energy, V (R)

electronic ground state

R
Which dashed line marks the defined zero, V (R) = 0, for the electronic energy of the
diatomic?
(a) A
(b) B
(c) C
(d) D
(e) E
2. If a hydrogen atom in the first excited state (n = 2) relaxes to the ground state
(n = 1) it will emit a photon to conserve energy. Which of the following is closest to
the wavelength ( ) of the emitted photon?
(a) 75 nm
(b) 122 nm
(c) 225 nm

(d) 500 nm
(e) 667 nm
(f) 1000 nm
3. You have a diatomic molecule. You measure the bond dissociation energy and find that
it is D0 = 400 kJ mol 1 . You measure the vibrational frequency using IR absorption
and find that there is an absorption line at = 2000 cm 1 . What is the electronic
energy, De , of the bond in this molecule?
(a) 200.0 kJ mol

(c) 400.0 kJ mol

(e) 425.2 kJ mol

(b) 387.4 kJ mol

(d) 412.0 kJ mol

(f) 440.0 kJ mol

4. Convert = 1000 cm 1 to kJ mol 1 using the following values for standard constants:
h = 6.626 10 34 J s, c = 2.998 108 m s 1 , NA = 6.022 1023 mol 1 .
(a) 1.084 10

(c) 1.083 10

(b) 1.181 10

kJ mol

kJ mol

kJ mol

(d) 1.196 kJ mol

(f) 108.4 kJ mol

(e) 11.96 kJ mol

(g) 1080 kJ mol

5. A ground-state hydrogen atom absorbs a photon of light that has a wavelength of 97.2
nm. It then gives o a photon that has a wavelength of 486 nm. What is the final
state of the hydrogen atom (n =?).
(a) 1
(b) 2
(c) 3
(d) 4
(e) 2.3
(f) 8
(g) 15
6. Given that = 2330 cm 1 and D0 = 78715 cm 1 for N2 (g), calculate the value of
De . Note that the value of is the position of an absorption peak in the IR/Raman
spectrum of N2 . This means that it is equal to the gap between quantized vibrational
levels. (Hint: See the lecture slide titled Dissociation Energy)

(a) 39940 cm

(b) 81045 cm

(c) 77540 cm

(d) 78715 cm

(e) 97560 cm

(f) 79880 cm

7. The energy dierence between the J = 0 and J = 1 rotational levels of carbon monoxide
(12 C16 O(g)) is = 1.153 105 MHz.
Calculate the energy dierence between J = 0 and J = 2 and give the answer in cm 1 .
(a) 2.306 105 cm

(b) 0.01154 cm
(c) 11.54 cm

(d) 3.459 1011 cm

(e) 11.54 102 cm

(f) 3.468 1010 cm

1
1
1

8. Calculate the degeneracy of the first 4 rotational levels of carbon monoxide:

(a) 0,1,3,5
(b) 0,2,4,6
(c) (1,1),(3,3)
(d) 1,3,6,9
(e) 2,3,5,8
(f) 1,3,5,7
(g) Cannot be determined, there are only three rotational levels possible.
(h) 1,2,3,4
9. Determine the number of various (translational, rotational, vibrational) degrees of
freedom of N2 :
(a) 3,2,1
(b) 6,2,1
(c) 3,3,0
(d) 3,1,2
(e) 5,3,1
(f) 6,1,1
(g) 6,2,2
10. Determine the number of various (translational, rotational, vibrational) degrees of
freedom of C2 H6 :

(a) 3,3,15
(b) 3,3,18
(c) 18,3,3
(d) 15,3,18
(e) 3,3,24
(f) 24,3,3
(g) 3,2,19
(h) 3,2,17