Problem Set 5 Solutions

Distributed: March 4, 2016

Due: March 11, 2016

McQuarrie Problems
6-5 and

Spacing of 16.72 cm−1 in the far infrared spectrum of H79 Br, what is moment of
inertia and internuclear separation?
e where B
The spectral spacing for rotational bands in a rotor is 2B e is the rotational
constant with units of wavenumbers. B e = h2 (Eq. 6.33) where I is the moment
8π cI
of inertia and c is the speed of light. Also, I = µr2 where µ is the reduced mass
and r is the bond length.

Using these equations,

( ) ( kg m2 )
h 6.6261 × 10−34 J · s ( m )
I= 2 = ( (
) 16.72 cm−1 ) s2
8π cB 8π 2 2.9979 × 108 ms J 100 cm
2

= 3.348 × 10−47 kg m2

m 79Br mH g
is the moment of inertia. For H79 Br, µ = m 79Br +mH
= 0.995116912 mol . Using
g g
78.9183371 mol and 1.00782503207 mol for bromine-79 and hydrogen, respectively.
We can calculate the bond length from the moment of inertia and this reduced mass:
√ v ( )
u (3.348 × 10−47 kg m2 ) 109 nm
I u
r=
µ
= t(
g )( )−1 ( kg
)
m
0.995116912 mol 6.0221 × 1023 1 mol 1000 g

= 0.1423 nm

Looking up the literature value, 0.14144 nm from McQuarrie’s table 6.1, we’re about
2 sig figs good. Maybe McQuarrie could have reported a better value for the peak
spacing on the spectrum.

6-37 Note that |Ylm (θ, ϕ)|2 is the same as (Ylm (θ, ϕ))∗ Ylm (θ, ϕ)—see Math Chapter A for details
on notation in complex numbers. |Ylm (θ, ϕ)|2 is not the normalization integral. Interpret your result.

The absolute values of the spherical harmonics (using |z| = zz ∗ ) for l = 1 (from

Boekelheide CH342: Quantum Chemistry

Problem Set 5 Solutions 2

table 6.5) are:

 +1     
Y (θ, ϕ)2 + Y10 (θ, ϕ)2 + Y −1 (θ, ϕ)2 =
1 1
√ 2 √ 2 √ 2
 3   3   3 
 +iϕ     −iϕ 
 sin θe  +  cos θ +  sin θe  =
 8π   4π   8π 
3 3 3
sin2 θ + cos2 θ + sin2 θ =
8π( 4π
) 8π
3 3 3
+ sin2 θ + cos2 θ =
8π 8π 4π
3 3 3 ( 2 )
sin2 θ + cos2 θ = sin θ + cos2 θ
4π 4π 4π | {z }
=1
3
= .
4π

The sum of the probability distributions of all the l = 1 spherical harmonics is uni-
form! This will let us build the px and py orbitals using the Y1+1 and Y1−1 spherical
harmonics later.

Problem 1: Orthogonality of d-orbitals

Spherical harmonic wavefunctions are eigenfunctions not only for the rigid rotor model, but also for the
angular behavior of the hydrogen atom. Show that dxz and dx2 −y2 listed in equation 7.32 on page 338
are orthogonal to one another. Hint: It may be easier to evaluate the spherical harmonics by working
in their general forms, then using definitions of the integrals of spherical harmonics to simplify the
expression.
( )
The d-orbitals using the spherical harmonics are dxz = √12 Y2−1 − Y2+1 and dx2 −y2 =
( ) ∫∞
√1 Y +2 + Y −2 (equation 7.32). The test for orthogonality will be ∗
2 2 2 −∞ dτ dxz dx2 −y 2 =
0, where the integral bounds represent all space for the spherical harmonics—θ :
0−π and ϕ : 0−2π—and the differential dτ = dθ sin θ dϕ. Because the integral will be
independent of the constants, we’ll neglect the normalizing constants. Keeping the
∫∞
spherical harmonics general, at the end we’ll use their orthogonality, −∞ dτ Ylm (θ, ϕ)∗ Ylm
′
′ (θ, ϕ) =
δll′ δmm′
∫ ∞ ∫ ∞ ( )∗ ( +2 )
dτ d∗xz dx2 −y2 = dτ Y2−1 − Y2+1 Y2 + Y2−2
−∞
∫−∞
∞ ( )
∗ ∗ ∗ ∗
= dτ Y2−1 Y2+2 + Y2−1 Y2−2 − Y2+1 Y2+2 − Y2+1 Y2−2
∫−∞
∞ ( )
∗ ∗ ∗ ∗
= dτ Y2−1 Y2+2 + Y2−1 Y2−2 − Y2+1 Y2+2 − Y2+1 Y2−2
−∞

= δ22  : 0 + δ δ 
 
: 0 − δ δ  : 0 − δ δ 
 :0 = 0

δ−1+2 22 −1−2 22 +1+2 22 +1−2

Because they are based on the orthongal spherical harmonics, the d-orbitals are

Boekelheide CH342: Quantum Chemistry

Problem Set 5 Solutions 3

also orthogonal.

Problem 2: Eigenfunctions of the Laplacian

Show that the following are eigenfunctions of the Laplacian operator and determine the eigenvalues:

I need to show that ∇2 f = af where a is some constant of the function f .

2.a: r−1 sin kr

( )
( −1
) 1 ∂ ∂ 1 ∂ ∂ 1 ∂2 ( )
∇ 2
r sin kr = 2 r2 + 2 sin θ + 2 2 r−1 sin kr
r ∂r ∂r r sin θ ∂θ ∂θ r sin θ ∂ϕ2
1 ∂ ∂ ( −1 )
= 2 r2 r sin kr
r ∂r ∂r
1 ∂ ∂ ( −1  :
) 0
+ 2 sin θ  r sin kr
r sin θ ∂θ ∂θ
1 ∂ ( −1
2 
:) 0
+ 2 2 2 r sin kr
r sin θ ∂ϕ
1 ∂ ( )
= 2 r2 kr−1 cos kr − r−2 sin kr
r ∂r
1 ∂
= 2 (kr cos kr − sin kr)
r ∂r 
 :0

1  
= 2 −k 2 r sin kr + k cos −
kr k cos kr 
r 
( )
= −k 2 r−1 sin kr .

The eigenvalue is −k 2 .

2.b: r−3 sin2 θ sin 2ϕ.

( )
( −3
) 1 ∂ ∂ 1 ∂ ∂ 1 ∂2 ( )
∇ 2
r 2
sin θ sin 2ϕ = 2 r2 + 2 sin θ + 2 2 r−3 sin2 θ sin 2ϕ
r ∂r ∂r r sin θ ∂θ ∂θ r sin θ ∂ϕ2
1 ∂ ∂ ( −3 2 )
= 2 r2 r sin θ sin 2ϕ
|r ∂r ∂r {z }
A
1 ∂ ∂ ( −3 2 )
+ 2
sin θ r sin θ sin 2ϕ
|r sin θ ∂θ ∂θ{z }
B
1 ∂ 2 ( −3 2 )
+ 2 2 2
r sin θ sin 2ϕ
r sin θ ∂ϕ
| {z }
C

Boekelheide CH342: Quantum Chemistry

Problem Set 5 Solutions 4

Let’s do this by terms, the r term first, A:

1 ∂ 2 ∂ ( −3 2 )
A= r r sin θ sin 2ϕ
r2 ∂r ∂r
1 ∂ ( )
= sin2 θ sin 2ϕ 2 r2 −3r−4
r ∂r
1 ∂ ( )
= sin2 θ sin 2ϕ 2 −3r−2
r ∂r
1 ( )
= sin θ sin 2ϕ 2 6r−3
2
r
( )
= sin θ sin 2ϕ 6r−5
2

=6r−5 sin2 θ sin 2ϕ.

The θ term, B:

1 ∂ ∂ ( −3 2 )
B= sin θ r sin θ sin 2ϕ
r2 sin θ ∂θ ∂θ
−3
r sin 2ϕ ∂
= 2 sin θ (2 cos θ sin θ)
r sin θ ∂θ
sin 2ϕ ∂ ( )
= 5 2 cos θ sin2 θ
r sin θ ∂θ
sin 2ϕ ( )
= 5 4 cos2 θ sin θ − 2 sin3 θ
r sin θ
sin 2ϕ ( )
= 5 4 cos2 θ − 2 sin2 θ
r
=4r−5 cos2 θ sin 2ϕ − 2r−5 sin2 θ sin 2ϕ

The ϕ term, C:

1 ∂ 2 ( −3 2 )
C= 2 2 ∂ϕ2 r sin θ sin 2ϕ
r sin θ
r−3 sin2 θ
= 2 2 (−4 sin 2ϕ)
r sin θ
= − 4r−5 sin 2ϕ

Combining A, B, and C, we get

A + B + C =6r−5 sin2 θ sin 2ϕ + 4r−5 cos2 θ sin 2ϕ − 2r−5 sin2 θ sin 2ϕ − 4r−5 sin 2ϕ
=4r−5 sin2 θ sin 2ϕ + 4r−5 cos2 θ sin 2ϕ − 4r−5 sin 2ϕ
:

−5
( 2
 2) 1
=4r sin 2ϕ sin 
θ + cos θ − 4r−5 sin 2ϕ

=4r−5 sin 2ϕ − 4r−5 sin 2ϕ
( )
= 0 = 0 r−3 sin2 θ sin 2ϕ .

The eigenvalue is 0.

Boekelheide CH342: Quantum Chemistry

Problem Set 5 Solutions 5

Problem 3: Quantum mechanics of the angular momentum vector L

Determine the allowed angles between the vector L and the z-axis for l = 1 and l = 2 using elementary
trigonometric relations between the vector length and its possible projections on the z-axis using an
approach similar to that on pages 290-295.
 
b 2 are ℏ2 l(l + 1)—so the eigenvalues of L
From equation 6.60, the eigenvalues of L b 
√
are ℏ l(l + 1)—and the eigenvalues of L b z are mℏ. From trigonometry, the allowed
mℏ m
angles will be cos θ = ℏ2 l(l+1)
= l(l+1)

For l = 1, m can be 1, 0, −1, so

z

l m m
θ (rad) θ (deg) +ħ
l(l+1) |L| = �2ħ
0
π
1 +1 1 4 45
π
1 0 0 90
y
2
1 −1 −1 3π
4 135 x -ħ

For l = 2, m can be 2, 1, 0, −1, −2, so

z
+2ħ
+ħ
m
l m l(l+1) θ (rad) θ (deg)

2 +2 2 0.196π 35.3 |L| = �6ħ

2 +1 1 0.366π 65.9
π 0
2 0 0 90.0
y
2
2 −1 −1 0.634π 114.1 -ħ x
2 −2 −2 0.804π 144.7
-2ħ

Problem 4: Microwave spectra

On the next page is the pure rotational spectrum of 12C18 O—you won’t be seeing a pure rotational
microwave spectrum in lab, so here’s your big chance! Assign the spectral features (ignore the weak
features which are due to the scarcer isotopes of carbon and oxygen). Estimate carefully from these data
using a ruler to measure the features the equilibrium bond length for CO using the rigid rotor model
(i.e. ignoring D, the centrifugal distortion constant).

The figure labeled with peak assignments (from NIST) and ∆ω’s is below. Ignoring
D, the peak spacing should be even, so the average ∆ω = 3.83 cm−1 = 2B, where

Boekelheide CH342: Quantum Chemistry

Problem Set 5 Solutions 6

B is the rotational constant. Following the same steps as in the first problem,
( ) ( kg m2 )
h 6.6261 × 10−34 J · s ( m )
I= 2 = ( (
) 1.92 cm−1 ) s2
8π cB 8π 2 2.9979 × 108 ms J 100 cm
2

= 1.46 × 10−46 kg m2

m 12C m 16O g
is the moment of inertia. For 12C16 O, µ= = 6.856208638001 mol . Using
m 12C +m 16O
g g
12 mol and 15.99491461956 mol for carbon-12 and oxygen-16, respectively. We can
calculate the bond length from the moment of inertia and this reduced mass:
√ v ( )
u (1.46 × 10−46 kg m2 ) 109 nm
I u ( )
= t(
g )( )
r=
µ 1 −1 kg m
6.856208638001 6.0221 × 1023
mol mol 1000 g

= 0.113 nm

which is exactly what McQuarrie reports (to our precision) in table 6.1.

Δω = 3.8 3.9 3.8 3.8 3.9 3.8

4-3 5-4 6-5 7-6 8-7 9-8 10-9

15.4 19.2 23.1 26.9 30.7 34.6 38.4

Figure 1. Far-infrared spectrum of CO showing rotational transitions. From (1).

Additional problems: Dirac notation2

∫∞
a. Write the following in Dirac notation i.e ψ(x) = |ψ⟩ and −∞
dx ψ ∗ (x) = ⟨ψ⟩. Notes: 1) x′ is used as a
dummy variable of integration. 2) Integrals are being written in the format you’re used to seeing in math and
in the format that is more common in physics.
∫ ∞
(i) f (x) = g(x) (iv) b ≡ ψ(x)
B ψ ∗ (x′ ) dx′
∫ ∞ −∞ ∫
∞
∂
(ii) c= m∗ (x′ )n(x′ ) dx′ (v) f (x) = m(x) m∗ (x′ )g(x′ ) dx′
−∞ ∂x −∞
∞ [
∑ ∫ ∞ ]
(iii) b
Af (x) = ϕn (x) ∗ ′ ′
ϕn (x )f (x ) dx ′

n=0 −∞

Boekelheide CH342: Quantum Chemistry

Problem Set 5 Solutions 7

Solutions:
(i) |f ⟩ = |g⟩ (iv) b ≡ |ψ⟩ ⟨ϕ|
B
∂
(ii) c = ⟨m|n⟩ (v) |f ⟩ = |m⟩ ⟨m|g⟩
∞
∂x
∑
(iii) Ab |f ⟩ = |ϕn ⟩ ⟨ϕn |f ⟩
n=0
b. Expand the following expressions into function-integral notation.
⟨   ⟩
 b
(i) |12 − 21⟩ (iii) 12 H  21 e.g. |1⟩ = ϕ1 (r1 ) |21⟩ = ϕ2 (r1 ) ϕ1 (r2 )
⟨   ⟩ ⟨   ⟩ ∫ ∞
 b  b b 2 (r) dr
(ii) |12 + 21⟩ (iv) 1 + 2 H 3 1 H 2 = ϕ∗1 (r) Hϕ
−∞
Solutions: ∫ ∞∫ ∞
(i) ϕ1 (r1 ) ϕ2 (r2 ) − ϕ2 (r1 ) ϕ1 (r2 ) (iii) b 2 (r1 ) ϕ1 (r2 ) dr1 dr2
ϕ∗1 (r1 ) ϕ∗2 (r2 ) Hϕ
∫−∞
∞
−∞

(ii) ϕ1 (r1 ) ϕ2 (r2 ) + ϕ2 (r1 ) ϕ1 (r2 ) (iv) (ϕ∗1 (r1 ) b 3 (r1 ) dr1
+ ϕ∗2 (r1 )) Hϕ
−∞
References
1. Barth P. F. Spectra of Atoms and Molecules, 2nd ed; Oxford University Press, 2005; p. 174. Accessed
at http://books.google.com/books?id=pW3uok6nITMC

2. From: Problem Set 1, Chem 120a, California Institute of Technology, T. Pascal (TA), 2008.

Boekelheide CH342: Quantum Chemistry