Problems 243

Now, because la_v) ex Iv - 1) and v::: 0, there must be some minimum value of v.
Let this value be vmin- By definition, then, we must have

Multiply from the left by a+ to get

o.
which says that Vmin = Furthermore, repeall:ed application of the raising operator a+
shows that v = 0, 1, 2, ... , so the energy eigenvalues of a harmonic oscillator are given
by liw(v + i),v = 0, 1, 2, ....
Now that we know the allowed energies, we can determine the corresponding wave
functions. Start with

a_IO) = iL 1/to = o (17)

Using the definition of a_,we have

1
-
,Ji.
- Cx + i [J)i/to = o
which, using equations 2, becomes

- 1 [ ( -J,ll'.t>) 1/2 x·. + ( -Ji ) 1/ 2 -d ] ifto' -- 0

Ji Ii µu> dx

or

di/to µ,w
- = - -Xi/to (18)
dx Ii

This equation can be integrated to give

where c is just a normalization constant. This result for ijt0 (x) is the same as that given
in Table 5.4 when you use the relation k = µw 2 . All the other eigenfunctions can be
obtained from ijt0 (x) by a repeated application of the raising operator a+ (Problem
5-45).

Problems
5-1. Show that the equation Md2 X/dt 2 = 0 (Equation 5.26) implies that the motion is uniform.

5-2. Verify that x (t) = A sin wt + B cos wt, where w = (k / m) 112 is a solution to Newton's
equation for a harmonic oscillator.
244 Chapter 5 I The Harmonic Oscillator and Vibrational Spectroscopy

5- 3. Verify that x(t) = C sin(wt + </>) is a solution to Newton's equation for a harmonic oscil-
lator.

5-4. The general solution for the classical harmonic oscillator is x(t) = C sin(wt + </>).Show
that the displacement oscillates between + c and - C with a frequency of w radian·s- 1 or
v = w /2rr cycle· s- 1• What is the period of the oscillations; that is, how long does it take to
undergo one cycle?

5-5. From Problem 5-4, we see that the period ofa harmonic vibration is r = l/v. The average
of the kinetic energy over one cycle is given by

(T) = -l
!'
lo ' - -
0
2 2
mw C cos 2 (wt + <P)dt
2

Show that (T} = E/2, where Eis the total energy. Show also that (V} = E/2, where the
instantaneous potential energy is given by

kC2
V = - sin 2 (wt + </>)
2

interpret the result (T} = (V}.

5-6. Consider two masses m 1 and m 2 in one dimension, interacting through a potential that
depends only upon their relative separation (x 1 - x 2), so that V(x 1, x2 ) = V (x 1 - x 2). Given
that the force acting upon the jth particle is fj = - (aV /oxj), show that / 1 = - f 2 . What
law is this?
Newton's equations for m 1 and m 2 are

d 2x
m,--= 1
- -ax,
av and
dt2

Now introduce center-of-mass and relative coordinates by

X= m 1X 1 + m2x2
M

where M = m 1 + m 2, and solve for x 1 and x 2 to obtain

and

Show that Newton's equations in these coordinates are

and
Problems 245
Now add these two equations to find

Interpret this result. Now divide the first equation by m 1 and the second by m 2 and subtract
to obtain

or

d 2x av
µ.,- = - -
dt2 ax
whereµ., = m 1m2 / (m 1 + m2 ) is the reduced mass. Interpret this result, and discuss how the
original two-body problem has been reduced to t\vo one-body problems.

5- 7. Extend the results of Problem 5- 6 to three d imensions. Realize that in three dimensions
the relative separation is given by

5-8. Show that the reduced mass of two equal masses, m, is m./2.

5-9. Example 5- 3 shows that a Maclaurin expansion of a Morse potential leads to

V(x) = Dfl2x 2 + · · ·
Given that D = 7.31 x w- 19 J·molecule- 1 andf:I = 1.81x10 10 m- 1 forHCl, calculatethe
force constant ofHCI. Plot the Morse potential for HCI, and plot the corresponding harmonic
oscillator potential on the same graph (cf. Figure 5.5).

5-10. Use the result of Example 5- 3 and Equation 5.39 to show that

l/ 2
fJ = 2rr CWobs ( :V )

Given that wobs = 2886 cm- 1 and D = 440.2 kJ · mo1- 1 for H 35CI, calculate .B. Compare
your result with that in Problem 5-9.

5- 11 . Carry out the Maclaurin expansion of the Morse potential in Example 5- 3 through tenns
in x 4 . Express y3 in Equation 5.30 in terms of D and (:I.

5-1 2. It turns out that the solution of the Schrodinger equation for the Morse potential can be
expressed as

G(v) - ( + 21) - --( + 21)

= We v WeXe V
2
246 Chapter 5 I The Harmonic Oscillator and Vibrational Spectroscopy

where

_ hcwe
x e -- - -
4D

Given that we = 2886 cm- 1 and D = 440.2 kJ ·mo1- 1 for H35 CI, calculate Xe and we.Xe.

5- 13. In the infrared spectrum of H 127I, there is an intense line at 2309 cm- 1• Calculate the
force constant ofH 127 I and the period of vibration ofH 127 I.

5- 14. The force constant of 35CI 35CI is 319 N · m- 1• Calculate the fundamental vibrational
frequency and the zero-point energy of 35CJ35CI.

5-15. The fundamental line in the infrared spectrum of 12C 160 occurs at 2143.0 cm- 1, and the
first overtone occurs at 4260.0 cm - 1. Calculate the values of We and XeWe for 12C 160 .

5-16. Using the parameters given in Table 5.1, calculate the fundamental and the first three
overtones ofH 79Br.

5- 17. The frequencies of the vibrational transitions in the anharmonic-oscillator approximation

are given by Equation 5.43. Show how the values of both We and XeWe may be obtained by
plotting Wobs/v versus (v + 1). Use this method and the data in Table 5.1 to determine the
values of We and XeWe for H35 Cl.

5- 18. The following data are obtained from the infrared spectrum of 127 I35Cl. Using the method
of Problem 5-17, determine the values of we and xewe from these data.

Transition Frequency/cm- 1

1 381.20
759.60
1135.00
4 1507.40
1877.00

5- 19. The vibrational term of a diatomic molecule is given to a good approximation by

where v is the vibrational quantmn number. Show that the spacing between the adjacent
levels is given by

= G(v + I) - G(v) = we{l - 2ie(v + I)} (I)

The diatomic molecule dissociates in the limit that 0. Show that the maximum
vibrational quantum number, Vmax• is given by
Problems 247
Use this result to show that the dissociation energy De of the diatomic molecule can be
written as

(2)

Referring to equation 1, explain how the constants We and Xe can be evaluated from a plot of
!J.G versus v + I. This type of plot is called a Birge-Sponerplot. Once the values ofWe and.Xe
are known, equation 2 can be used to determine the dissociation energy of the molecule.
Use the following experimental data for H 2 to calculate the dissociation energy, De.

v G(v)/cm- 1 v G(v)/cm- 1

0 4161.12 7 26 830.97
8087.11 8 29123.93
2 11 782.35 9 31 .150.19
3 15 250.36 lO 32 886.85
4 18497.92 11 34 301.83
5 21 505.65 12 35 351.0 I
6 24 287.83 13 35 972.97

Explain why your Birge-Sponer plot is not linear for high values of v. How does the value
of De obtained from the Birge-Sponer analysis compare with the experimental value of
38 269.48 cm- 1?

5-20. An analysis of the vibrational spectrum of the ground-electronic-state homonuclear

diatomic molecule C2 gives We = 1854.71 cm- 1 and we.Xe = 13.34 cm- 1• Suggest an ex-
perimental method that can be used to determine these spectroscopic parameters. Use the
expression derived in Problem 5- 19 to determine the number of vibrational levels for the
ground state ofC2.

5-21. Verify that 1/1 1(x) and 1/!2(x) given in Table 5.4 satisfy the Schrodinger equation for a
harmonic oscillator.

5- 22. Show explicitly for a harmonic oscillator that 1/!o(O is 01ihogonal to 1/1 1Ce), 1/!2(e), and
(e) m
1/!3 and that 1/1 1(0 is orthogonal to 1/!2 and 1/!J(O (see Table 5.4).
5-23. To normalize the harmonic-oscillator wave f1mctions and calculate various expectation
values, we must be able to evaluate integrals .of the fonn

v = 0, 1, 2, ...

We can simply either look them up in a table of integrals or continue this problem. First,
show that
248 Chapter 5 I The Harmonic Osci llator and Vibrational Spectroscopy

The case v = 0 can be handled by the following trick. Show that the square of ! 0 (a) can be
written in the form

oo looo dxdye-a(x + y)
l
2 2
I 2 (a) = 4
0 0

Now convert to plane polar coordinates, Jetting

r2 = x2 + y2 and dxdy = rdrdB

Show that the appropriate limits of integration are 0 r < oo and 0 e /2 and that

It(a) = 4 lo
r 12dB loroo drre-' 2
11

which is elementary and gives

2 rt I rt
I 0 (a) = 4 · - · - = -
2 2a a

or

l/ 2
/ 0 (a) =( ; )

Now prove that the I v(a) may be obtained by repeated differentiation of ! 0 (a) with respect
to a and, in particular, that

dvlo(a) = (- WI (a)
da V V

Use this result and the fact that / 0 (a) = (rt/a) 112 to generate / 1(a), I2(a), and so forth.

5-24. Prove that the product of two even functions is even, that the product of two odd functions
is even, and that the product of an even and an odd function is odd.

5 -25. Prove that the derivative of an even (odd) function is odd (even).

5-2 6. Show that

1
00
5 Ii
(x 2} = 1/f2 (x)x 21/f2(x)dx = - -----ip
- 00 2 (µ,k)

for a harmonic oscillator. Note that (x 2} 112 is the square root of the mean of the square of
the displacement (the root-mean-square displacement) of the oscillator.

5-27. Show that (p} = 0 and that

for a harmonic oscillator.

Problems 249
5-28. Use the result of the previous two problems to show that £ 2 = 5hv/2 .

5- 29. Prove that

(T} = ( V(x)} = Ev
2

for a one-dimensional harmonic oscillator for v = 0 and v = I.

5-30. Show that the eigenfunctions and eigenvalues of a three-dimensional harmonic oscillator
whose potential energy is

V (x, y, z) =
2
+2 y
y2 +
2 z
z2

are

where

(u = x, y, or z)

and

where

Discuss the degeneracy of this system when the oscillator is isotropic-that is, when
kx = ky = kz. Make a diagram like that shown in Figure 3.6.

5-31. There are a number of general relations between the Hermite polynomials and their
derivatives (which we wi LI not derive). Some of these are

dHv(O (1') - H (t)

v '> v+ I '>

and
250 Chapter 5 I The Harmonic Osci llator and Vibrational Spectroscopy

Such connecting relations are called formulas. Verify these formulas explicitly
using the first few Hermite polynomials given in Table 5.3.

5-32. Use the recursion formulas for the Hermite polynomials given in Problem 5-31 to show
that (p) = 0 and (p2) = n(µ,k) lf 2 (v + Rememberthat the momentum operator involves
a differentiation with respect to x' note.

5-33. It can be proved generally that

(x 2 ) =- 1( + -I) = - -
a
v
2
Ii
(µ,k) 112
(v +-.I)
2

and that

2
(x 4 ) = - 3 2 (2v2 + 2v + 1) = -3/i (2v 2 + 2v + I)
4a 4µ,k

for a harmonic oscillator. Verify these formulas explicitly for the first two states of a
harmonic oscillator.

5-34. This problem is similar to Problem 3-39. Show that the harmonic-oscillator wave func-
tions are alternately even and odd functions of x because the Hamiltonian operator obeys
ii (x) = ii (- x). Define a reflection operator Rby
Ru(x) = u( - x)

Show that R is linear and that it commutes with ii. Show also that the eigenvalues of R
are ± I. What are its eigenfunctions? Show that the harmonic-oscillator wave functions are
eigenfunctions of k Note that they are eigenfunctions of both ii and k What does this
observation say about ii and R?

5-35 . Use Ehrenfest's theorem (Problem 4-44) to show that (Px) does not depend upon time
for a one-dimensional harmonic oscillator.

5-36. Figure 5.13 compares the probability distribution associated with 1{1 10 (0 to the classical
distribution. (See also Problem 3-18.) This problem illustrates what is meant by the classical
distribution. Consider

x(t) = A sin(wt + ¢)
which can be written as

wt = sin - I ( - ¢>

Now

(I)
Problems 25 1

.. FIGURE 5.13
The probability distribution function of a
harmonic oscillator in the v = 10 state. The
dashed line is that for a classical harmonic
oscillator with the same energy. The vertical
-5 -3 - l 3 5 lines ate ±4.6 represent the extreme limits
of the classical harmonic motion.

This equation gives the time that the oscillator spends between x and x + dx. We can
convert equation l to a probability distribution in x by dividing by the time that it takes
for the oscillator to go from - A to A. Show that this time is TC /w and that the probability
distribution in x is

dx
p(x)dx = (2)
rc-JA 2 - x 2

Show that p(x) is normalized. Why does p(x) achieve its maximum value atx =±A? Now
e
use the fact that = a 112x ' where Ci = (k µ,/ /i2) 112 ' to show that

p(e)de = J (3)
TC aA - e2
e
Show that the limits of are ± (aA 2 ) 112 =± (21) 112 , and compare this result to the vertical
lines shown in Figure 5.13 .Hint: You need to use the fact that kA 2/2 = £ 10 (n = 10). Finally,
plot equation 3 and compare your result with the curve in Figure 5.13 .

5-37. We can use the harmonic-oscillator wav·e function to ilJustrate tunneling, a strictly
quantum-mechancial property. The probability that the displacement of a harmonic os-
cillator in its ground state lies between x and x + dx is given by

l/ 2
2
P(x) dx = dx =
(
;. ) e-ax dx (1)

The energy of the oscillator in its ground state is (/'i/2)(k/µ.,) 112 • Show that the greatest
displacement that this oscillator can have classically is its amplitude

Ii ] l/ 2 1
(2)
A = [ (kµ.,) 112 = et 112
252 Chapter 5 I The Harmon ic Oscillator and Vibrational Spectroscopy

According to equation I, however, there is a nonzero probability that the displacement of the
oscillator will exceed this classical value and tunnel into the classically forbidden region.
Show that this probability is given by

1
-tf - 1/ 2

- oo
P (x ) dx + 1. 00

P (x ) dx =
1T
f
JL
00
2
e-z dz (3)

The integral here cannot be evaluated in closed form but occurs so frequently in a number
of different fields (such as the kinetic theory of gases and statistics) that it is well tabulated
under the name complementaty error.function, erfc(x), which is defined as

2 [00
erfc(x) = 7r l/2 Jx e- z2 dz (4)

By referring to tables, it can be found that the probability that the displacement of the
molecule will exceed its classical amplitude is 0. 16.

5- 38. Problem 5- 37 shows that although a classical harmonic oscillator has a fixed amplitude, a
quantum-mechanical harmonic oscillator does not. We can, however, use (x 2 } as a measure
of the square of the amplitude, and, in particular, we can use the square root of (x 2}, the
root-mean-square value of x , Arms = Xrrms = (x 2} 112, as a measure of the amplitude. Show
that

Ii ] 1/2 ( h ) 1/ 2
A - x - -
rms - rms - [ 2(µ,k) l/2 - 4 rrcwobstl

for the ground state of a harmonic oscillator. Thus, we can calculate (x 2} 112 in terms of &obs·
Show that A rms = 7.58 pm for H 35 CI. The bond length ofHCI is 127 pm, and so we can see
that the root-mean-square amplitude is only about 5% of the bond length. This is typical of
diatomic molecules.

5-39. The fi.mdamental vibrational frequency of H 79 Br is 2.63 x 103 cm- 1 and l is 141 pm.
Calculate the root-mean-square displacement in the ground state and compare your result
to l.

5-40. In this problem, we'll calculate the fraction of diatomic molecules in a particular vibra-
tional state at a temperature Tusing the harmonic-oscillator approximation. A fundamental
equation of physical chemistry is the Boltzmann distribution, which says that the number
of molecules with an energy Ej is proportional to e-Ei/k8 T, where k3 is the Boltzmann
constant and T is the kelvin temperature. Thus, we write

N
io:.e -E'·/kllT

Using the fact that L Nj = N , show that the fraction of molecules wi th an energy Ej is
given by

Q ( T)
Problems 253
The denominator here, Q (T), is called a partition function. Show that the partition function
of a harmonic oscillator [E j = (j + is

00

Hint: You need to use the geometric series L xj = ( 1- x)- 1 for lx l < I. Now show that
j =O

and, in particular, that

Now show that / 0 l at300K fora typical molecule, with we = LOOO cm- 1. Plot the fraction
of molecules in the jth vibrational state at T = 300 K.

5-41. Calculate the fraction of HBr molecules in the ground vibrational state at 300 Kand
2000 K. Take We to be 2650 cm- 1•

5-42. D etermine the number of translational, rotational, and vibrational degrees of freedom in

(b) ocs

5-43. In this problem, we will prove the so-called quantum-mechanical virial theorem. Start
with H1{! = £1{!, where

fi2 2,
+ V(x, y, z)
A

H = - - \l
2m

Using the fact that fl is a Hermitian operator, show that

f 1/l"[il, A]1/ld< = o (l)

where A is any linear operator. Choose A to be

A = - ili
A (
x-a +y-a +z-a) (2)
ox ay az
and show that

A A

[H , A] = ili
(

x-av av av)
ax +y-oy +z-oz
iii
- - (P2 + P2 + P)
m x
A

.Y
A
2
z
A

." ( x-av +y-av +z-av) -

= tn ."TA
2tn
ax ay oz
254 Chapter 5 I The Harmon ic Oscillator and Vibrational Spectroscopy

where Tis the kinetic energy operator. Now use equation l and show that

av av
(x -ax +y -ay + z-oz
av) A

= 2(T} (3)

Equation 3 is the quantum-mechanical virial theorem.

5-44. Use the virial theorem (Problem 5-43) to prove that (f} = ( V} = E /2 for a ha1monic
oscillator.

5-45. Use the fact that

A -
aift - -
I
+ " ..J2
[(f.1,{J))
-
Ii
2
l/ xA- (Ii-
µ,w
2
)l/ pA]

References
Barrow, G. Molecular Spectmscopy. McGraw-Hill: New York, 1962.
Brown, J.M. Molecular S]Jectroscopy. Oxford University Press: New York, 1998.
Wi lson, E. B., Decius, J. C., Cross, P. C. Molecular Vibrations. Dover Publications: Mineola, NY,
1955.
Banwell, C. N., McCash, E. M. Fundamentals ofMolecular Spectroscopy, 4th ed. McGraw-Hill: New
York, 1944.
Hotlas, J. Michael. Molecular Spectmscopy, 4th ed. Wiley & Sons: New York, 2004.
Hotlas, J.M. Basic Atomic and Molecular Spectmscopy. Wiley & Sons: New York, 2002.
Herzberg, G. Molecular Spectra and Molecular Structure: Spectra ofDiatomic Molecules, 2nd ed.
Krieger Publishing: Malabar, FL, 1989.
Hanis, D. C., Bertolucci, M. D. Symmetry and Sj1ectmscopy: An Introduction to Vibrational and
Electronic Spectroscopy. Dover Publications: Mineola, NY, 1989.