11

Quantum Mechanics
CHAPTER and Atomic Structure

LAIDLER . MEISER . SANCTUARY

Physical Chemistry
Electronic Edition

Problems and Solutions

Chapter 11: Quantum Mechanics and Atomic Structure Electromagnetic Radiation and Wave Motion

Chapter 11
Electromagnetic Radiation and Wave Motion
11.1. Calculate, for light of 325 nm wavelength,
a. the frequency;
b. the wavenumber;
c. the photon energy in J, eV, and kJ mol–1; and
d. the momentum of the photon.
Solution
11.2. A pulsar in the Crab Nebula, NP 0532, emits both radio pulses and optical pulses. A radio pulse is observed at 196.5 Mhz. Calculate
a. the corresponding wavelength;
b. the energy of the photon in J, eV and J mol–1; and
c. the momentum of the photon.
Solution
11.3. The potassium spectrum has an intense doublet with lines at 766.494 nm and 769.901 nm. Calculate the frequency difference
between these two lines.
Solution
11.4. Suppose that the position y of a particle that travels along the Y axis of a coordinate system is given by

⎡ 3π rad ⎛ t ⎞ ⎤
y ( t ) = y0 sin ⎢ ⎜ ⎟+C⎥
⎣ 5 ⎝s⎠ ⎦

What is the frequency of the wave motion?

Solution
11.5. A mass of 0.2 kg attached to a spring has a period of vibration of 3.0 s.
a. What is the force constant of the spring?
b. If the amplitude of vibration is 0.010 m, what is the maximum velocity?
Solution

11-2
Chapter 11: Quantum Mechanics and Atomic Structure Particles and Waves

*11.6. If the average energy associated with a standing wave of frequency ν in a cavity is

hν
ε=
exp ( hν /kBT ) −1

deduce the expression for the low-frequency limit of the average energy associated with the standing wave.
Solution
Particles and Waves
11.7. A sodium lamp of 50-watt power emits yellow light at 550 nm. How many photons does it emit each second? What is the
momentum of each photon?
Solution
11.8. The threshold frequency ν0 for emission of photoelectrons from metallic sodium was found by Millikan, Phys. Rev., 7, 1916, p. 362,
to be 43.9 × 1013 s–1. Calculate the work function for sodium. A more recent value, for a carefully outgassed sample of sodium, is 5.5
× 1013 s–1. What work function corresponds to that value?
Solution
11.9. Calculate the value of the de Broglie wavelength associated with
a. an electron moving with a speed of 6.0 × 107 m s–1 (this is the approximate velocity produced by a potential difference of 10 kV).
b. an oxygen molecule moving with a speed of 425 m s–1 at 0 °C.
c. an α-particle emitted by the disintegration of radium, moving at a speed of 1.5 × 107 m s–1.
d. an electron having a speed of 2.818 × 108 m s–1.
Solution
11.10. Consider a colloidal particle with a mass of 6 × 10–16 kg. Suppose that its position is measured to within 1.0 nm, which is about the
resolving power of an electron microscope. Calculate the uncertainty in the velocity and comment on the significance of the result.
Solution

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Chapter 11: Quantum Mechanics and Atomic Structure Particles and Waves

11.11. Calculate the velocity and the de Broglie wavelength of an electron accelerated by a potential of
a. 10 V,
b. 1 kV, and
c. 1 MV.
Solution
*11.12. The group velocity of a wave is given by the equation

dν
vg =
d (1/ λ )

Prove that the group velocity of a de Broglie particle wave is equal to the ordinary velocity of the particle.
Solution
11.13. Photoelectric experiments show that about 5 eV of energy are required to remove an electron from platinum.
a. What is the maximum wavelength of light that will remove an electron?
b. If light of 150 nm wavelength were used, what is the velocity of the emitted electron?
Solution
11.14. Calculate the kinetic energy of an electron that has a wavelength of (a) 10 nm, (b) 100 nm.
Solution
11.15. Calculate the de Broglie wavelength of (a) an α-particle (a helium nucleus) accelerated by a field of 100 V, and (b) a tennis ball
served at 220 km h–1. (An α-particle has a mass of 6.64 × 10–27 kg and a diameter of about 10–15 m. A standard tennis ball has a mass
of 55.4 g and a diameter of 6.51 cm.)
Solution

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Chapter 11: Quantum Mechanics and Atomic Structure Quantum-Mechanical Principles

Quantum-Mechanical Principles
11.16. Assume that the three real functions ψ1, ψ2, and ψ3 are normalized and orthogonal. Normalize the following functions:
a. ψ1 + ψ2
b. ψ1 – ψ2
c. ψ1 + ψ2 + ψ3
1 3
d. ψ 1 – ψ2 + ψ3
2 2

Solution
11.17. Is the function Ae–ax an eigenfunction of the operator d2/dx2? If so, what is the eigenvalue?
Solution
11.18. Prove that m1 must be integral in order for the function

Φ = sin m1φ

to be an acceptable wave function.

Solution
11.19. The energy operator for a time-dependent system (Table 11.1) is

∂
i˜
∂t
A possible eigenfunction for the system is
Ψ(x, y, z, t) = ψ(x, y, z) exp(–2πiEt/h)
Show that Ψ Ψ*, the probability density, is independent of time.
Solution

11-5
Chapter 11: Quantum Mechanics and Atomic Structure Quantum-Mechanical Principles

*11.20. Prove that the momentum operator corresponding to px is a Hermitian operator.

Solution
11.21. Which of the following functions is an eigenfunction of the operator d/dx?

a. k d. exp(kx)
2
b. kx e. exp(kx2)
c. sin kx f. exp(ikx)

(k is a constant, and i is the square root of minus one.) Give the eigenvalue where appropriate.
Solution
11.22. Figure 11.20 shows the angular momentum vectors for 1 = 2 and for m = 2, 1, 0, –1, –2. In each case, calculate the angles the
vectors make with the Z axis.
Solution

11.23. Show that the one-electron wave functions ψnlm are also eigenfunctions of the operator ( Lˆ2x + Lˆ2y ). What physical property
(observable) is associated with this operator?
Solution
11.24. Explain why the Heisenberg uncertainty principle would be violated if the harmonic oscillator ground-state energy were zero.
Solution
Particle in a Box
11.25. Calculate the lowest possible energy for an electron confined in a cube of sides equal to
a. 10 pm and
b. 1 fm (1 femtometre = 10–15 m).
The latter cube is the order of magnitude of an atomic nucleus; what do you conclude from the energy you calculate about the
probability of a free electron being present in a nucleus?
Solution

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Chapter 11: Quantum Mechanics and Atomic Structure Quantum-Mechanical Principles

11.26. A particle is moving in one dimension between x = a and x = b. The potential energy is such that the particle cannot be outside these
limits and that the wave function in between is
ψ = A/x
a. Determine the normalization constant A.
b. Calculate the average value of x.
Solution
11.27. An electron is confined in a one-dimensional box 1 nm long. How many energy levels are there with energy less than 10 eV? How
many levels are there with energy between 10 and 100 eV?
Solution
11.28. Determine whether the eigenfunctions obtained in Section 11.6 for a particle in a one-dimensional box are eigenfunctions for the
momentum operator. If they are, obtain the eigenvalues; if they are not, explain why.
Solution
*11.29.Treat the three-dimensional particle in a box of sides a, b, and c by analogy with the treatment in Section 11.6. Assume the potential
to be zero inside the box and infinite outside, and proceed by the following steps:
a. Write the basic differential equation that must be solved for the three-dimensional problem.
b. Separate the equation from (a) into terms involving X(x), Y( y), and Z(z).
c. Determine the expressions for X, Y, and Z.
d. Obtain the expression (Eq. 11.150) for the total energy.
Solution
11.30. What is the quantum-mechanical probability of finding the particle in a one-dimensional “box” in the middle third of the “box”?
Derive an expression that shows how this quantity depends on the quantum number n.
Solution

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Chapter 11: Quantum Mechanics and Atomic Structure Quantum-Mechanical Principles

.31. The classical probability for finding a particle in the region x to x + dx in a one-dimensional box of length a is dx/a.
a. Derive the classical probability for finding the particle in the middle third of the box.
b. Show that as n → ∞, the quantum probability obtained in the previous problem becomes identical to the classical result.
Solution
*11.32. Problem 11.25 is concerned with the calculation of the minimum energy for an electron confined in a cube. Another approach to the
problem is to consider, on the basis of the uncertainty principle (Eq. 11.60), the uncertainty in the energy if the uncertainty in the
position is equal to the length of the side of the cube. Calculate ΔE for a cube of sides equal to
a. 10 pm and
b. 1 fm (10–15 m),
and compare the results with the minimum energies found for Problem 11.25.
Solution
*11.33. Prove that any two wave functions for a particle in a one-dimensional box of length a are orthogonal to each other; that is, they
obey the relationship
a
∫ψ
0
ψ n dx = 0, m ≠ n
m

Solution
11.34. Use the trial function Ψ = x(a – x) and Eq. 11.247 to calculate an energy for a particle in a one-dimensional box of length a.
Solution
11.35. a. At a node, a wave function passes through zero. For the problem of the particle in a box, how many nodes are there for n = 2 and
n = 3?
b. From the expression for the radial function for the 3s electron (Table 11.4), obtain expressions for the position of the radial nodes
(i.e., the nodes in the solution of the radial equation) in terms of Z and a0.
Solution

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Chapter 11: Quantum Mechanics and Atomic Structure Vibration and Rotation

Vibration and Rotation

11.36. The vibration frequency of the N2 molecule corresponds to a wave number of 2360 cm–1. Calculate the zero-point energy and the
energy corresponding to v = 1.
Solution
*11.37. If a rigid body rotates in the XY plane, about the Z axis, the angular momentum operator is

∂
Lˆ = – i ˜
∂φ

(see Figure 11.15). If the moment of inertia is I, what is the energy operator?
(For additional problems dealing with molecular vibrations and rotations, see Chapter 13.)
Solution
The Atom
11.38. Calculate the ionization energy of the hydrogen atom on the basis of the Bohr theory.
Solution
11.39. Calculate, on the basis of the Bohr theory, the linear velocity of an electron (mass = 9.11 × 10–31 kg) in the ground state of the
hydrogen atom. To what de Broglie wavelength does this velocity correspond? Deduce an equation for the de Broglie wavelength, in
a Bohr orbit of quantum number n, with Z = 1, in terms of a0 and n. What is the ratio of the circumference of a Bohr orbit of
quantum number n to the de Broglie wavelength?
Solution
11.40. For a hydrogenlike atom (a one-electron system with a charge number of Z), find the radius of the sphere on which the probability of
finding the 1s electron is a maximum. Compare the result to the expression of Eq. 11.44.
Solution

11-9
Chapter 11: Quantum Mechanics and Atomic Structure The Atom

*11.41. Calculate the reduced masses of the hydrogen and deuterium atoms, using the following masses for the particles:

Electron: 9.1095 × 10–31 kg

Proton: 1.6727 × 10–27 kg
Deuterium nucleus: 3.3434 × 10–27 kg

a. Explain qualitatively what effect the different reduced masses will have on the Bohr radii and therefore on the positions of the
lines in the atomic spectra.
b. The Balmer spectrum of hydrogen has a line of wavelength 656.47 nm. Deduce the wavelength of the corresponding line in the
spectrum of deuterium.
Solution
11.42. Calculate the wavelength and energy corresponding to the n = 4 to n = 5 transition in the hydrogen atom.
Solution
11.43. Calculate, in joules and in atomic units, the potential energy of an electron in the n = 2 orbit of the hydrogen atom.
Solution
11.44. The first ionization energy of the Li atom is 5.39 eV. Estimate an effective nuclear charge Zeff for the valence electron in the Li
atom.
Solution
11.45. The first ionization energy of the Na atom is 5.14 eV. Estimate the effective nuclear charge Zeff for the valence electron in the Na
atom.
Solution
*11.46. Use Slater’s method (Section 11.13) to determine the effective nuclear charge for
a. a 3s electron in the chlorine atom,
b. a 3p electron in the phosphorus atom, and
c. the 4s electron in the potassium atom.
Solution

11-10
Chapter 11: Quantum Mechanics and Atomic Structure The Atom

*11.47. A normalized Slater orbital for the 1s orbital in the helium atom is
3/ 2
1 ⎛ Z eff ⎞
ψ 1s = ⎜ ⎟ exp(– Z eff r/a0 )
π ⎝ a0 ⎠

where Zeff is the effective charge number. It leads to the following expression for the energy

e2 ⎛ 2 27 ⎞
E= ⎜ Z eff − Z eff ⎟ .
a0 ⎝ 8 ⎠

Treat Zeff as a variation parameter, and calculate a minimum energy in terms of e and a0. Why is the optimum value of Zeff different
from the actual charge number?
Solution
*11.48. Use the wave function for the 1s orbital of the hydrogen atom, given in Table 11.5, to obtain an expression for the probability that
the electron lies between the distance r and r + dr from the nucleus. (Use spherical polar coordinates, for which the volume element
is r2 dr sin θ dθ dφ .)

Solution
*11.49. Unsöld’s theorem (Section 11.8) states that, for a given value of l, the sum of the values of

∑ [Θ
l ,m
l ,m (θ )Φ m (φ )]2

is independent of θ and φ , i.e., is a constant. Write all these functions for the 2p orbitals (see Tables 11.2 and 11.3), and show that
their sum shows no angular dependence.
Solution

11-11
Chapter 11: Quantum Mechanics and Atomic Structure Essay Questions

Essay Questions
11.50. With emphasis on the physical significance, explain precisely what is meant by a normalized wave function.
11.51. Explain clearly the relationship between the Heisenberg uncertainty principle and the question of whether two operators commute.
11.52. Give an account of the main principles underlying the variation method in quantum mechanics.
11.53. Discuss the reasons for abandoning the Bohr theory of the atom.

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Chapter 11: Quantum Mechanics and Atomic Structure Solutions

Solutions
11.1. Calculate, for light of 325 nm wavelength,
a. the frequency;
b. the wavenumber;
c. the photon energy in J, eV, and kJ mol–1; and
d. the momentum of the photon.
Solution:
Given: λ = 325 nm

Required: ν , ν , ε , p

a. The frequency is calculated from Eq. 11.1

λν = c
c
ν=
λ
2.998 ×108 m s −1
ν=
325 ×10−9 m
ν = 9.224 615 385 ×1014 s −1
ν = 9.22 ×1014 s −1

b. The wavenumber is given by the inverse of the wavelength.

1
ν=
λ
1
ν=
325 ×10−7 cm
ν = 30 769.230 77 cm −1
ν = 30.8 ×104 cm −1

c. The photon energy is given by in the Key Equations section as

11-13
Chapter 11: Quantum Mechanics and Atomic Structure Solutions

E = hν

( )(
ε = 6.626 ×10−34 J s 9.224 615 385 ×1014 s −1 )
ε = 6.112 230 15 ×10−19 J
ε = 6.11×10−19 J

In electron volts we get,

6.112 230 15 × 10−19 J

ε=
1.602 × 10−19 J eV −1
ε = 3.815 374 628 eV
ε = 3.82 eV

In kJ per mole we get,

ε = ( 6.112 230 15 ×10−19 J )( 6.022 ×1023 mol−1 )

ε = 368 078.499 9 J mol−1
ε = 368 kJ mol−1

d. The momentum is given by Eq. 11. 55

h
λ=
p
6.626 × 10−34 J s
p=
325 ×10−9 m
p = 2.038 769 23 × 10−27 kg m s −1
p = 2.04 × 10−27 kg m s −1

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11-14
Chapter 11: Quantum Mechanics and Atomic Structure Solutions

11.2. A pulsar in the Crab Nebula, NP 0532, emits both radio pulses and optical pulses. A radio pulse is observed at 196.5 Mhz. Calculate
a. the corresponding wavelength;
b. the energy of the photon in J, eV and J mol–1; and
c. the momentum of the photon.
Solution:
Given: ν = 196.5 Mhz

Required: λ , ε , p

e. The wavelenth is calculated from Eq. 11.1

λν = c
c
λ=
ν
2.998 × 108 m s −1
λ=
196.5 ×106 s −1
λ = 1.525 699 746 m
λ = 1.526 m

f. The photon energy is given by in the Key Equations section as

E = hν

( )(
ε = 6.626 ×10−34 J s 196.5 ×106 s −1 )
ε = 1.302 009 ×10−25 J
ε = 1.302 ×10−25 J

In electron volts we get,

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Chapter 11: Quantum Mechanics and Atomic Structure Solutions

1.302 009 × 10−25 J

ε=
1.602 × 10−19 J eV −1
ε = 8.127 397 004 ×10−7 eV
ε = 8.127 ×10−7 eV

In kJ per mole we get,

ε = (1.302 009 ×10−25 J )( 6.022 ×1023 mol−1 )

ε = 0.078 406 982 J mol−1
ε = 7.841×10−2 kJ mol−1

g. The momentum is given by Eq. 11. 55

h
λ=
p
6.626 × 10−34 J s
p=
1.525 699 746 m
p = 4.342 925 28 ×10−34 kg m s −1
p = 4.343 ×10−34 kg m s −1

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11-16
Chapter 11: Quantum Mechanics and Atomic Structure Solutions

11.3. The potassium spectrum has an intense doublet with lines at 766.494 nm and 769.901 nm. Calculate the frequency difference
between these two lines.
Solution:

Given: λ1 = 766.494 nm, λ2 = 769.901 nm

Required: Δν

The frequency difference is calculated by converting the wavelengths to their respective frequencies. Using Eq. 11.1,
λν = c
c
ν=
λ
2.998 × 108 m s −1
ν1 =
766.494 × 10−9 m
ν 1 = 3.911 315 679 ×1014 s −1
2.998 ×108 m s −1
ν2 =
769.901×10−9 m
ν 2 = 3.894 007 152 ×1014 s −1
Δν = ν 1 −ν 2
Δν = 3.911 315 679 × 1014 s −1 − 3.894 007 152 ×1014 s −1
Δν = 1.730 852 735 × 1012 s −1
Δν = 1.731×1012 s −1

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11-17
Chapter 11: Quantum Mechanics and Atomic Structure Solutions

11.4. Suppose that the position y of a particle that travels along the Y axis of a coordinate system is given by

⎡ 3π rad ⎛ t ⎞ ⎤
y ( t ) = y0 sin ⎢ ⎜ ⎟+C⎥
⎣ 5 ⎝s⎠ ⎦

What is the frequency of the wave motion?

Solution:
Given: equation above
Required: ν

To find the frequency, we compare this equation to that given by Eq. 11.6,

y = A sin (ωt + δ )

Angular frequency is defined in Eq. 11.4 as

ω = ( 2π rad )ν

Therefore frequency is obtained as,

ω
ν=
2π rad
3 π 5 rad s −1
ν=
2 π rad
3 −1
ν= s
10
ν = 0.3 s −1

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11-18
Chapter 11: Quantum Mechanics and Atomic Structure Solutions

11.5. A mass of 0.2 kg attached to a spring has a period of vibration of 3.0 s.

a. What is the force constant of the spring?
b. If the amplitude of vibration is 0.010 m, what is the maximum velocity?
Solution:
Given: m = 0.2 kg, τ = 3.0 s, A = 0.010 m

Required: kh , vmax

a. The force constant of the spring can be determined using Eq. 11.15
1 kh
ν=
2π m
kh = m ( 2πν )
2

The period is the inverse of the frequency, thus,

1
τ=
ν
1
ν=
τ
2
⎛ 1 ⎞
kh = 0.2 kg ⎜ 2π ⎟
⎝ 3.0 s ⎠
kh = 0.877 298169 kg s −2
kh = 0.88 N m −1

b. The maximum velocity is determined by taking the first derivative of Eq. 11.6.
y = A sin (ωτ + δ )
dy
vmax = = ω A cos (ωτ + δ )
dτ

Since cos θ ≤ 1 for all angles, it follows that the maximum velocity is,

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Chapter 11: Quantum Mechanics and Atomic Structure Solutions

vmax = ω A

Substituting ω for Eq. 11.14 we can finally solve.

kh
vmax = A
m
0.877 298169 kg s −2
vmax = ( 0.010 m )
0.2 kg
vmax = 0.020 943 951 m s −1
vmax = 2.1×10−2 m s −1

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11-20
Chapter 11: Quantum Mechanics and Atomic Structure Solutions

*11.6. If the average energy associated with a standing wave of frequency ν in a cavity is

hν
ε=
exp ( hν /kBT ) −1

deduce the expression for the low-frequency limit of the average energy associated with the standing wave.
Solution:
Given: expression above
Required: expression for the standing wave
The low-frequency limit can be obtained by use of the series expansion

x2
e = 1 + x + + ...
x

2!

hν
When x is small, we can make the approximation e x = 1 + x , where x = .
kBT

Thus, when hν << kBT ,

hν
ε= = kBT
hν
1+ −1
kBT

Electromagnetic waves are transverse waves having two degrees of freedom. The value kBT is divided between the two degrees of freedom.

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11-21
Chapter 11: Quantum Mechanics and Atomic Structure Solutions

11.7. A sodium lamp of 50-watt power emits yellow light at 550 nm. How many photons does it emit each second? What is the
momentum of each photon?
Solution:
Given: P = 50 W, λ = 550 nm

Required: E / s, p

We first determine the energy emitted in each photon using E = hν . The frequency is calculated from Eq. 11.1

λν = c
c
ν=
λ
hc
E=
λ
( 6.626 ×10 −34
Js ) ( 2.998 ×10
8
m s −1 )
E=
550 × 10−9 m
E = 3.611 772 36 ×10−19 J

Recall that 1W = 1 J s −1 , therefore we can determine the number of photons emitted each second by dividing power by energy of a photon.

P
E /s =
E
50 J s −1
E /s =
3.611 772 36 ×10−19 J
E / s = 1.384 361886 × 1020 s −1
E / s = 1.4 ×1020 s −1

The momentum is given by Eq. 11. 55

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Chapter 11: Quantum Mechanics and Atomic Structure Solutions

h
λ=
p
6.626 × 10−34 J s
p=
550 × 10−9 m
p = 1.204 727 27 ×10−27 kg m s −1
p = 1.20 × 10−27 kg m s −1

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Chapter 11: Quantum Mechanics and Atomic Structure Solutions

11.8. The threshold frequency ν0 for emission of photoelectrons from metallic sodium was found by Millikan, Phys. Rev., 7, 1916, p. 362,
to be 43.9 × 1013 s–1. Calculate the work function for sodium. A more recent value, for a carefully outgassed sample of sodium, is 5.5
× 1013 s–1. What work function corresponds to that value?
Solution:

Given: ν = 43.9 ×1013 s –1 , ν recent = 5.5 × 1013 s –1

Required: w
The work function, w, is given in Eq. 11.37,

1
hν = mu 2 + w
2

1
When the kinetic energy, mu 2 is zero, we get the expression hν 0 = w , with ν 0 as the threshold frequency. Solving for w we get,
2

w = hν 0

(
w = 6.626 × 10−34 J s ) ( 43.9 ×1013
s –1 )
w = 2.908 814 × 10−19 J
w = 2.91× 10−19 J

In eV, work is given as,

2.908 814 × 10−19 J

w=
1.602 × 10−19 J eV −1
w = 1.815 739 076 eV
w = 1.82 eV

For the more recently determined value the work is,

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Chapter 11: Quantum Mechanics and Atomic Structure Solutions

(
w = 6.626 ×10−34 J s ) ( 5.5 ×10
13
s –1 )
w = 3.644 3 × 10−20 J
w = 3.6 ×10−20 J
3.644 3 × 10−20 J
w=
1.602 ×10−19 J eV −1
w = 0.227 484 394 5 eV
w = 0.23 eV

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Chapter 11: Quantum Mechanics and Atomic Structure Solutions

11.9. Calculate the value of the de Broglie wavelength associated with

a. an electron moving with a speed of 6.0 × 107 m s–1 (this is the approximate velocity produced by a potential difference of 10 kV).
b. an oxygen molecule moving with a speed of 425 m s–1 at 0 °C.
c. an α-particle emitted by the disintegration of radium, moving at a speed of 1.5 × 107 m s–1.
d. an electron having a speed of 2.818 × 108 m s–1.
Solution:
Given: see above

Required: λde Broglie

The de Broglie wavelength is given by Eq. 11. 56,

h h
λ= =
p mu

a. The mass of an electron is m = 9.11× 10−31 kg , therefore

λ=
( 6.626 ×10 J s )
−34

( 9.11×10 kg )( 6.0 ×10 m s )

−31 7 –1

λ = 1.212 221 ×10−11 m

λ = 1.2 ×10−11 m = 12 pm

b. The mass of O2 is obtained from its molar mass divided by the number of molecules per mole (Avogadro’s constant).

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Chapter 11: Quantum Mechanics and Atomic Structure Solutions

M O2 = 2 × 15.9994 g mol –1
M O2 = 31.9988 g mol –1
31.9988 g mol –1 1 kg
mO2 = ×
6.022 × 10 mol
23 –1
1000 g
6.626 ×10−34 J s
λ=
⎛ 31.9988 g mol –1 1 kg ⎞
× ⎟ ( 425 m s )
–1
⎜
⎝ 6.022 ×10 mol
23 –1
1000 g ⎠
λ = 2.934 063 85 ×10−11 m
λ = 2.93 ×10−11 m = 29.3 pm

c. An alpha particle consist of two protons and two neutrons and can be written as He2+. Hence, its molar mass is 4 g mol-1. We can then
solve in a similar manner as part b.
4 g mol –1 1 kg
mα = ×
6.022 × 10 mol
23 –1
1000 g
6.626 × 10−34 J s
λ=
⎛ 4 g mol –1 1 kg ⎞
× ⎟ (1.5 ×10 m s )
7 –1
⎜
⎝ 6.022 × 10 mol
23 –1
1000 g ⎠
λ = 6.650 295 33 ×10−15 m
λ = 6.7 ×10−15 m = 6.7 fm

d. The mass of an electron is m = 9.11× 10−31 kg , therefore

λ=
( 6.626 ×10 J s )
−34

( 9.11×10 kg )( 2.818 ×10

−31 8
m s –1 )
λ = 2.581 024 14 ×10−12 m
λ = 2.58 ×10−12 m = 2.58 pm

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Chapter 11: Quantum Mechanics and Atomic Structure Solutions

11.10. Consider a colloidal particle with a mass of 6 × 10–16 kg. Suppose that its position is measured to within 1.0 nm, which is about the
resolving power of an electron microscope. Calculate the uncertainty in the velocity and comment on the significance of the result.
Solution:

Given: m = 6 ×10 –16 kg, Δq = 1.0 nm

Required: Δu , comment on the result

The uncertainty of the velocity is given in Eq. 11.61

˜
Δq Δu ≥
2m

h
=
Since ˜ , we can substitute and solve for Δu .
2π

h
Δq Δu ≈
4π m
h
Δu =
4π mΔq

Δu =
( 6.626 ×10 −34
J s = kg m 2 s −1 )
4π ( 6 ×10 –16
kg )(10−9 m )
Δu = 8.788 005 44 ×10 –11 m s −1
Δu = 9 ×10 –11 m s −1

With this uncertainty in velocity, the position of the particle one second later would be uncertain to 2 × 9 × 10 –11 m s −1 or 0.18 nm. This is
only 0.18% of the diameter of the particle, and the uncertainty principle therefore does not present a serious problem for particles of this
magnitude. For particles of molecular sizes, the uncertainty is much greater.

Back to Problem 11.10 Back to Top

11-28
Chapter 11: Quantum Mechanics and Atomic Structure Solutions

11.11. Calculate the velocity and the de Broglie wavelength of an electron accelerated by a potential of
a. 10 V,
b. 1 kV, and
c. 1 MV.
Solution:
Given: potentials above

Required: u, λde Broglie

To solve this problem, we use the procedure given in Example 11.2.

When a charge, q, is placed in an electric potential field, V, it experiences a force depending upon its position and starts to accelerate and
pick up kinetic energy. This is given by Ek = qV.
a. For a potential of 10 V,
Ek = eV
( )
Ek = 1.602 ×10 –19 C (10 V )
Ek = 1.602 ×10 –18 J

1 2
The kinetic energy is mu and therefore
2

2 ×1.602 ×10−18 J
u=
9.11×10−31 kg
u = 1875 370.435 m s −1
u = 1.9 ×106 m s −1

From Eq. 11.56, the de Broglie wavelength λ is,

11-29
Chapter 11: Quantum Mechanics and Atomic Structure Solutions

h h
λ= =
p mu

λ=
( 6.626 ×10 J s )
−34

( 9.11×10 kg )(1875 370.435 m s )

−31 −1

λ = 3.878 340 98 ×10−10 m

λ = 3.9 ×10−10 m = 3.9 ×102 pm

b. Using the same procedure above, we obtain,

Ek = (1.602 ×10 –19 C ) (1000 V )
Ek = 1.602 ×10 –16 J
2 ×1.602 ×10−16 J
u=
9.11×10−31 kg
u = 18 753 704.35 m s −1
u = 1.9 ×107 m s −1

The de Broglie wavelength λ is therefore,

h
λ=
mu

λ=
( 6.626 ×10 J s )
−34

( 9.11×10 kg )(18 753 704.35 m s )

−31 −1

λ = 3.878 340 98 ×10−11 m

λ = 3.9 ×10−11 m = 3.9 ×10 pm

c. Using the same procedure above, we obtain,

11-30
Chapter 11: Quantum Mechanics and Atomic Structure Solutions

Ek = (1.602 ×10 –19 C )(106 V )

Ek = 1.602 ×10 –13 J
2 ×1.602 ×10−13 J
u=
9.11×10−31 kg
u = 593 044 203.2 m s −1
u = 5.9 ×108 m s −1

The de Broglie wavelength λ is therefore,

h
λ=
mu

λ=
( 6.626 ×10 J s )
−34

( 9.11×10 kg )( 593 044 203.2 m s )

−31 −1

λ = 1.226 439 1×10−12 m

λ = 1.2 ×10−12 m = 1.2 pm

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11-31
Chapter 11: Quantum Mechanics and Atomic Structure Solutions

*11.12. The group velocity of a wave is given by the equation

dν
vg =
d (1/ λ )

Prove that the group velocity of a de Broglie particle wave is equal to the ordinary velocity of the particle.
Solution:
Given: group velocity
Required: proof

1 2
From the expression E = hν and the definition of kinetic energy mu , a particle of mass m has a frequency of,
2

E
ν=
h
mu 2
ν=
2h

Substituting the de Broglie wavelength, Eq. 11.56, into the newly acquired expression for frequency, we can eliminate the velocity term.

h
λ=
mu
h
u=
mλ
2
m⎛ h ⎞
ν= ⎜ ⎟
2h ⎝ mλ ⎠
h
ν=
2mλ 2

The group velocity is therefore,

11-32
Chapter 11: Quantum Mechanics and Atomic Structure Solutions

dν
vg =
d (1/ λ )
⎛ h ⎞
d⎜ ⎟
2mλ 2 ⎠
vg = ⎝
d (1/ λ )

⎛ h ⎞⎛ 1 ⎞
vg = 2 ⎜ ⎟⎜ ⎟
⎝ 2m ⎠ ⎝ λ ⎠
h
vg =
mλ

And from above,

vg = u

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11-33
Chapter 11: Quantum Mechanics and Atomic Structure Solutions

11.13. Photoelectric experiments show that about 5 eV of energy are required to remove an electron from platinum.
a. What is the maximum wavelength of light that will remove an electron?
b. If light of 150 nm wavelength were used, what is the velocity of the emitted electron?
Solution:
Given: E = 5 eV, Pt

Required: λmax , u

a. The minimum frequency such that an electron can be removed from platinum is given by,
E = hν min
E
ν min =
h

And the corresponding maximum wavelength is therefore given by Eq. 11.1. Solving for λmax we get,

λν = c
c
λ=
ν
ch
λ=
E

λ=
( 2.998 ×10 8
m s −1 ) ( 6.626 ×10 −34
J s )
( 5 ×1.602 ×10 −19
J )
λ = 2.479 993 508 ×10−7 m
λ = 2.480 ×10−7 m = 248 nm

b. The wavelength 150 nm corresponds to a frequency of

11-34
Chapter 11: Quantum Mechanics and Atomic Structure Solutions

λν = c
c
ν=
λ

ν=
( 2.998 ×10 8
m s −1 )
(150 ×10 −9
m )
ν = 1.998 666 667 ×1015 s −1

And to an energy of

( )(
E = 6.626 ×10−34 J s 1.998 666 667 × 1015 s −1 )
E = 1.324 316 53 × 10−18 J

The excess energy is therefore the difference between this value and the energy required to remove an electron from platinum.

(
Eexcess = 1.324 316 53 × 10−18 J − 5 ×1.602 × 10−19 J )
Eexcess = 5.233165 33 × 10−19

1 2
The kinetic energy is mu and therefore
2

2 × 5.233165 33 ×10−19 J
u=
9.11×10−31 kg
u = 1 071859.934 m s −1
u = 1.072 ×106 m s −1

Back to Problem 11.13 Back to Top

11-35
Chapter 11: Quantum Mechanics and Atomic Structure Solutions

11.14. Calculate the kinetic energy of an electron that has a wavelength of (a) 10 nm, (b) 100 nm.
Solution:
Given: λ = 10 nm, λ = 100 nm

Required: Ek

h
From the de Broglie equation, Eq. 11.56, λ = and therefore
p

h
p= .
λ
The kinetic energy Ek is given by

p2
Ek =
2m
Therefore,

h2
Ek =
2mλ 2
a. Solving for the kinetic energy where λ = 10 nm gives,
( 6.626 ×10 J s )
2
−34

Ek =
2 ( 9.11×10 kg )(10 ×10 m)
2
−31 −9

Ek = 2.409 652 91×10−21 J

Ek = 2.4 ×10−21 J

b. Solving for the kinetic energy where λ = 100 nm gives,

11-36
Chapter 11: Quantum Mechanics and Atomic Structure Solutions

( 6.626 ×10 J s )
2
−34

Ek =
2 ( 9.11×10 kg )(100 × 10 m)
2
−31 −9

Ek = 2.409 652 91×10−23 J

Ek = 2.4 ×10−23 J

Back to Problem 11.14 Back to Top

11-37
Chapter 11: Quantum Mechanics and Atomic Structure Solutions

11.15. Calculate the de Broglie wavelength of (a) an α-particle (a helium nucleus) accelerated by a field of 100 V, and (b) a tennis ball
served at 220 km h–1. (An α-particle has a mass of 6.64 × 10–27 kg and a diameter of about 10–15 m. A standard tennis ball has a mass
of 55.4 g and a diameter of 6.51 cm.)
Solution:

Given: a. Vα = 100 V, mα = 6.64 × 10 –27 kg, d = 10 –15 m

b. utennis ball = 220 km h –1 , mtennis ball = 55.4 g, d = 6.51 cm

Required: λde Broglie

d. For a potential of 100 V, the energy of an alpha particle is,

Ek = eV
( )
Ek = 2 × 1.602 ×10 –19 C (100 V )
Ek = 3.204 × 10 –17 J

1 2
The kinetic energy is mu and therefore
2

2 × 3.204 ×10 –17 J

u=
6.64 ×10−27 kg
u = 98 237.479 m 66s −1

The de Broglie wavelength λ is therefore,

h
λ=
mu

λ=
( 6.626 ×10 J s ) −34

( 6.64 ×10 kg )( 98 237.479 m 66s )

−27 −1

λ = 1.015 79516 ×10−12 m

λ = 1.02 ×10−12 m

11-38
Chapter 11: Quantum Mechanics and Atomic Structure Solutions

Thus the wavelength is about 1000 times larger than the diameter of the particle.
e. We convert the velocity of the tennis ball to m s-1 and then determine the wavelength.
103 m h
u = 220 km h −1 × ×
km 3600 s
u = 61.11111111 m s −1

λ=
( 6.626 ×10 J s )
−34

( 55.4 ×10 kg )( 61.11111111 m s )

−3 −1

λ = 1.957 13817 ×10−34 m

λ = 1.96 ×10−34 m

This is about 3 ×1032 times smaller than the diameter of the tennis ball.

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11-39
Chapter 11: Quantum Mechanics and Atomic Structure Solutions

11.16. Assume that the three real functions ψ1, ψ2, and ψ3 are normalized and orthogonal. Normalize the following functions:
a. ψ1 + ψ2
b. ψ1 – ψ2
c. ψ1 + ψ2 + ψ3
1 3
d. ψ 1 – ψ2 + ψ3
2 2

Solution:
Given: three real functions ψ1, ψ2, and ψ3 ; all normalized and orthogonal
Required: Normalize a – d
a. The normalization condition for any function ψ is given by Eq. 11. 89 as,
∫ψ *ψ dτ = 1
In other words, to normalize the function ψ 1 +ψ 2 , we multiply by its conjugate and set its integral equal to 1. Since we are told that all three
functions are real, the conjugate of ψ 1 +ψ 2 is simply ψ 1 +ψ 2 . When solving we introduce a factor N.

Reading sections titled Normalization and Normalization Condition will help further understand normalization.

∫ N (ψ +ψ ) N (ψ +ψ ) dτ = 1
1 2 1 2

N ∫ (ψ + ψ ) dτ = 1
2 2
1 2

N ⎡ ∫ψ dτ + 2 ∫ψ ψ dτ + ∫ψ dτ ⎤ = 1
2 2 2
⎣ 1 ⎦ 1 2 2

The first and last integrals are equal to unity since ψ1 and ψ2 are normalized, as given in the problem. The second integral is equal to zero
( 2∫ψ ψ dτ = 0) since the wave function is orthogonal. Eq. 11.111 defines orthogonality as,
1 2

∫ψ ψ dτ = 0
*
1 2

This leads to the result,

11-40
Chapter 11: Quantum Mechanics and Atomic Structure Solutions

N 2 [1 + 0 + 1] = 1
2N 2 = 1
1
N=
2

The normalized wave function is therefore,

1
(ψ 1 +ψ 2 )
2

b. We apply the same rationale as above to solve for the normalized wave functions in the following cases.
N 2 ∫ (ψ 1 −ψ 2 ) dτ = 1
2

N 2 ⎡ ∫ψ 12 dτ − 2 ∫ψ 1ψ 2 dτ + ∫ψ 2 2 dτ ⎤ = 1
⎣ ⎦
N [1 − 0 + 1] = 1
2

2N 2 = 1
1
N=
2
1
(ψ 1 −ψ 2 )
2

c.

11-41
Chapter 11: Quantum Mechanics and Atomic Structure Solutions

N 2 ∫ (ψ 1 +ψ 2 + ψ 3 ) dτ = 1
2

N 2 ⎡ ∫ψ 12 dτ + ∫ψ 2 2 dτ + ∫ψ 32 dτ + 2∫ψ 1ψ 2 dτ + 2∫ψ 1ψ 3 dτ + 2∫ψ 2ψ 3 dτ ⎤ = 1

⎣ ⎦
N [1 + 1 + 1 + 0 + 0 + 0] = 1
2

3N 2 = 1
1
N=
3
1
(ψ 1 +ψ 2 +ψ 3 )
3

d.
2
⎛ 1 3 ⎞
N ∫ ⎜⎜ψ 1 −
2
ψ 2 + ψ 3 ⎟⎟ dτ = 1
⎝ 2 2 ⎠
⎡ 1 3 2 2 3 2 3 ⎤
N 2 ⎢ ∫ψ 12 dτ + ∫ψ 2 2 dτ + ∫ψ 32 dτ − ∫ ψ 1ψ 2 dτ − ∫ ψ 1ψ 3dτ − ∫ψ 2ψ 3dτ ⎥ = 1
⎣ 2 2 2 2 2 ⎦
N [1 + 1 + 1 + 0 + 0 + 0] = 1
2

3N 2 = 1
1
N=
3
1 ⎛ 1 3 ⎞
⎜⎜ψ 1 − ψ 2 + ψ 3 ⎟⎟
3⎝ 2 2 ⎠
⎛ 1 1 1 ⎞
⎜ ψ1 − ψ2 + ψ3 ⎟
⎝ 3 6 2 ⎠

Back to Problem 11.16 Back to Top

11-42
Chapter 11: Quantum Mechanics and Atomic Structure Solutions

11.17. Is the function Ae–ax an eigenfunction of the operator d2/dx2? If so, what is the eigenvalue?
Solution:
Given: Ae–ax
Required: answer the question, find eigenvalue if applicable
If Ae–ax is an eigenfunction of d2/dx2, an operation on Ae–ax twice by d/dx will give the orginal function multiplied by a constant.

d
dx
( )
Ae – ax = − Aae – ax

d
dx
( )
− Aae – ax = Aa 2 e – ax

Since the operation returns the original function multiplied by a constant, a2, then Ae–ax is an eigenfunction of the operator d2/dx2 with
eigenvalue a2.

eigenvalue = a 2

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11-43
Chapter 11: Quantum Mechanics and Atomic Structure Solutions

11.18. Prove that m1 must be integral in order for the function

Φ = sin mlφ

to be an acceptable wave function.

Solution:
Given: function above
Required: proof
For the wave function to be single valued,

Φ = sin mlφ must equal Φ = sin ( ml (φ + 2π ) )

Using the double angle formulas, we obtain the expression for Φ = sin ( ml (φ + 2π ) ) as,

Φ = sin ( mlφ + 2π ml )
sin ( A + B ) = sin A cos B + sin B cos A
Φ = sin mlφ cos 2π ml + sin 2π ml cos mlφ

For this to equal sin mlφ , cos 2π ml must be 1 and therefore 2π ml = 0 . This is only true if ml is an integer value.

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11-44
Chapter 11: Quantum Mechanics and Atomic Structure Solutions

11.19. The energy operator for a time-dependent system (Table 11.1) is

∂
i˜
∂t
A possible eigenfunction for the system is
Ψ(x, y, z, t) = ψ(x, y, z) exp(–2πiEt/h)
Show that Ψ*Ψ, the probability density, is independent of time.
Solution:
Given: energy operator, Ψ(x, y, z, t)
Required: Show that Ψ*Ψ, the probability density, is independent of time.
First of all, we do not consider the energy operator to solve this problem.
We are given eigenfunction,

Ψ ( x, y, z , t ) = ψ ( x, y, z ) e –2π iEt / h

Its conjugate is given by,

Ψ * ( x, y, z , t ) = ψ * ( x, y, z ) e 2π iEt / h

The probability density is therefore,

Ψ * Ψ = ψ *e –2π iEt / hψ e 2π iEt / h

Ψ * Ψ = ψ *ψ e0
Ψ * Ψ = ψ *ψ

The exponential term, containing the time dependence is cancelled out, leaving only theψ functions which is simply a function of x, y and z.
Therefore the probability density is independent of time.
Back to Problem 11.19 Back to Top

11-45
Chapter 11: Quantum Mechanics and Atomic Structure Solutions

*11.20. Prove that the momentum operator corresponding to px is a Hermitian operator.

Solution:
Given: px
Required: proof
The momentum operator px is given in Table 11.1 as,

∂
−i˜
∂x
The definition for a Hermitian operator is given by Eq. 11.106,

∫ψ Fˆ ψ 1 d τ = ∫ ψ 1 ( Fˆ ψ 2 ) * d τ
*
2

Where F̂ is an operator and ψ 1 and ψ 2 are any two functions.

Using the momentum operator and the functionsψ ( x ) and φ ( x ) for clarity we must prove that,

⎛ ∂ψ ⎞ ⎛ ∂φ ⎞
∫ φ *⎜⎝ −i˜ ⎟ dx = ∫ψ ⎜ −i˜
∂x ⎠ ⎝
⎟ * dx
∂x ⎠

Using integration by parts on the left side gives,

⎛ ∂ψ ⎞ ∞ ⎛ ∂φ * ⎞
⎟ dx = − i˜ [φ *ψ ] −∞ − ∫−∞ψ ⎜ −i˜
∞
∫ φ * ⎜ −i˜
⎝ ∂x ⎠ ⎝ ∂x ⎠
⎟ dx

11-46
Chapter 11: Quantum Mechanics and Atomic Structure Solutions

The first term is zero since all wave functions must asymptotically go to zero at ±∞ . The second term is
∞ ⎛ ∂φ * ⎞
= 0 − ∫ ψ ⎜ −i˜ ⎟ dx
−∞
⎝ ∂x ⎠
∞ ⎛ ∂φ * ⎞
= ∫ ψ ⎜ −i˜ ⎟ dx
−∞
⎝ ∂x ⎠

Which is the same as the right hand side as the equation given above. Therefore operator is Hermitian.

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11-47
Chapter 11: Quantum Mechanics and Atomic Structure Solutions

11.21. Which of the following functions is an eigenfunction of the operator d/dx?

a. k d. exp(kx)
2
b. kx e. exp(kx2)
c. sin kx f. exp(ikx)

(k is a constant, and i is the square root of minus one.) Give the eigenvalue where appropriate.
Solution:
Given: a – d
Required: eigenfunction of d/dx, eigenvalues
As stated in problem 11.17, if the operation returns the original function multiplied by a constant, the function is an eigenfunction.

dk
a. = 0 = 0(k )
dx
Therefore k is an eigenfunction of the operator d/dx with eigenvalue = 0
dkx 2
b. = 2kx
dx
kx2 is not an eigenfunction of the operator d/dx.
d sin kx
c. = k cos kx
dx
sinkx is not an eigenfunction of the operator d/dx.
de kx
d. = ke kx
dx
e kx is an eigenfunction of the operator d/dx with eigenvalue = k
2
dekx 2
e. = 2kxekx
dx
kx 2
e is not an eigenfunction of the operator d/dx.

11-48
Chapter 11: Quantum Mechanics and Atomic Structure Solutions

deikx
f. = ikeikx
dx
e is an eigenfunction of the operator d/dx with eigenvalue = ik
ikx

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11-49
Chapter 11: Quantum Mechanics and Atomic Structure Solutions

11.22. Figure 11.20 shows the angular momentum vectors for 1 = 2 and for m = 2, 1, 0, –1, –2. In each case, calculate the angles the
vectors make with the Z axis.
Solution:
Given: Figure 11.20
Required: θ
From the figure, we see that the length L of each vector is given by

L = 2 ( 2 + 1)˜
L = 6˜

The Z component in each case is given by

ml ˜

ml
Using trigonometry, we see that the cosine of each angle is therefore cos θ = .
6

Solving for the case where ml = 2 ,

⎛ 2 ⎞
θ = cos −1 ⎜ ⎟
⎝ 6⎠
θ = 35.264 389 68
θ = 35.3

Using the procedure as above, we obtain the following results.

ml 2 1 0 −1 −2
θ / deg 35.3 65.9 90.0 114.1 144.7

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11-50
Chapter 11: Quantum Mechanics and Atomic Structure Solutions

11.23. Show that the one-electron wave functions ψnlm are also eigenfunctions of the operator ( Lˆ2x + Lˆ2y ). What physical property
(observable) is associated with this operator?
Solution:

Given: ψnlm and ( Lˆ2x + Lˆ2y ).

Required: proof
From Eq. 11. 203 we are given that

Lˆ2 = Lˆ2x + Lˆ2y + Lˆ2z

Therefore, by rearranging we get

Lˆ2x + Lˆ2y = Lˆ2 − Lˆ2z

To show that the one-electron wave functions ψnlm are also eigenfunctions of this operator, we perform the following,

( Lˆ + Lˆ )ψ
2
x
2
y nlm ( )
= Lˆ2 − Lˆ2z ψ nlm

Then from Eq. 11. 208 and Eq. 11.211, we substitute the eigenvalues below

= ( l ( l + 1) ˜ 2 − ml 2˜ 2 )ψ nlm
= ( l ( l + 1) − ml 2 ) ˜ 2ψ nlm

Therefore ψnlm are eigenfuntions of the operator Lˆ2x + Lˆ2y with eigenvalues ( l ( l + 1) − ml 2 ) ˜ 2 .

The operator Lˆ2x + Lˆ2y corresponds to x 2 + y 2 and the equation,

x2 + y 2 = a2 ,
Which is the equation for a circle with radius a. The physical property corresponding to the operator is thus the square of the radius of the
base of the angular momentum vector as it rotates about the Z axis. (see Figure 11.20)

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11-51
Chapter 11: Quantum Mechanics and Atomic Structure Solutions

11.24. Explain why the Heisenberg uncertainty principle would be violated if the harmonic oscillator ground-state energy were zero.
Solution:
Given: situation above
Required: explain
If the harmonic oscillator ground state energy were zero, the implications is that the kinetic and potential energies are both zero (since
neither can take on negative values). Therefore the momentum is exactly zero. Also, from the nature of the potential-energy function, the
total energy can only be zero at x = 0. Therefore, this leads to a situation where we know the values of the momentum and position
simultaneously and exactly. This is a violation of the Uncertainty Principle.

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11-52
Chapter 11: Quantum Mechanics and Atomic Structure Solutions

11.25. Calculate the lowest possible energy for an electron confined in a cube of sides equal to
a. 10 pm and
b. 1 fm (1 femtometre = 10–15 m).
The latter cube is the order of magnitude of an atomic nucleus; what do you conclude from the energy you calculate about the
probability of a free electron being present in a nucleus?
Solution:
Given: electron in a box, a = 10 pm, a = 1 fm
Required: E
From Eq. 11.151 the expression for the energy of a particle in a box is given by

h2
E= (n12 + n22 + n32 )
8ma 2

For the lowest energy possible we set n1 = n2 = n3 = 1 . Using m as the mass of an electron, we solve for E in each case.

3 ( 6.626 × 10−34 J s )
2

E=
8 ( 9.11× 10−31 kg ) a 2

a.

a = 10 ×10−12 m
a = 1.0 ×10−11 m
3 ( 6.626 × 10−34 J s )
2

E=
8 ( 9.11×10−31 kg )(1.0 × 10−11 m )
2

E = 1.807 239 68 ×10−15 J

E = 1.8 ×10−15 J

In eV,

11-53
Chapter 11: Quantum Mechanics and Atomic Structure Solutions

1.807 239 68 × 10−15 J

E=
1.602 ×10−19 J eV −1
E = 11 281.146 58 eV
E = 1.1×104 eV

b.
a = 1×10−15 m

( )
2
3 6.626 × 10−34 J s
E=
( )( )
2
8 9.11× 10−31 kg 1× 10−15 m
E = 1.807 239 682 × 10−7 J
E = 1.81×10−7 J
1.807 239 682 × 10−7 J
E=
1.602 ×10−19 J eV −1
E = 1.128114 658 × 1012 eV
E = 1.13 ×1012 eV

The latter energy is so large that one electron would not remain in the nucleus, but would be emitted as a β particle.

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11-54
Chapter 11: Quantum Mechanics and Atomic Structure Solutions

11.26. A particle is moving in one dimension between x = a and x = b. The potential energy is such that the particle cannot be outside these
limits and that the wave function in between is
ψ = A/x
a. Determine the normalization constant A.
b. Calculate the average value of x.
Solution:
Given: x = a, x = b, ψ = A / x

Required: A, x

a. The normalization condition is given by Eq. 11.89

∫ψ *ψ dτ = 1
For this wave function, the normalization condition becomes,
b
∫ ψ *ψ dx = 1
a

Solving for A we obtain,

11-55
Chapter 11: Quantum Mechanics and Atomic Structure Solutions

b
∫ ( A / x )( A / x ) dx = 1
a

b A2
∫a x2
dx = 1
b
⎡ 1⎤
A2 ⎢ − ⎥ = 1
⎣ x ⎦a
⎡ 1 1⎤
A2 ⎢ − + ⎥ = 1
⎣ a b⎦
⎡b − a ⎤
A2 ⎢ =1
⎣ ab ⎥⎦
ab
A2 =
b−a
ab
A=
b−a

b. To find the average value of x we use Eq.11.104

∞

F≡ F = ∞
∫−∞
ψ *( Fˆ ψ ) dτ

∫ ψ *ψ dτ−∞

ab ⎛ 1 ⎞
Since we have normalized the function, ψ = ⎜ ⎟ , the denominator becomes 1 and we can solve as,
b−a ⎝ x⎠

11-56
Chapter 11: Quantum Mechanics and Atomic Structure Solutions

∞
x = ∫ ψ *( xψ ) dx
−∞

b ab ⎛ 1 ⎞ ab ⎛ 1 ⎞
x =∫ ⎜ ⎟x ⎜ ⎟ dx
a b−a ⎝ x ⎠ b−a ⎝ x⎠
ab b 1
b − a ∫a x
x = dx

ab
[ln x ]a
b
x =
b−a
ab b
x = ln
b−a a

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11-57
Chapter 11: Quantum Mechanics and Atomic Structure Solutions

11.27. An electron is confined in a one-dimensional box 1 nm long. How many energy levels are there with energy less than 10 eV? How
many levels are there with energy between 10 and 100 eV?
Solution:
Given: a = 1 nm, E = 10 eV, E = 100 eV

Required: n
To calculate the nth energy level, we use Eq. 11.149

n 2 ( 6.626 × 10−34 J s )
2

En =
8 ( 9.11×10−31 kg )(1×10−9 m )
2

En = 6.024 132 27 ×10−20 n 2 J

6.024 132 27 ×10−20 n 2 J
En =
1.602 × 10−19 J eV −1
En = 0.376 038 219 2 n 2 eV
En
n=
0.376 038 219 2 eV

At 10 eV,

10 eV
n=
0.376 038 219 2 eV
n = 5.156 844 15
n≈5

Thus, levels 1 through 5 have energies less than 10 eV.

At 100 eV,

11-58
Chapter 11: Quantum Mechanics and Atomic Structure Solutions

100 eV
n=
0.376 038 219 2 eV
n = 16.307 373 05
n ≈ 16

Thus, levels 6 through 16 have energies between 10 eV and 100 eV.

Back to Problem 11.27 Back to Top

11-59
Chapter 11: Quantum Mechanics and Atomic Structure Solutions

11.28. Determine whether the eigenfunctions obtained in Section 11.6 for a particle in a one-dimensional box are eigenfunctions for the
momentum operator. If they are, obtain the eigenvalues; if they are not, explain why.
Solution:
Given: Section 11.6
Required: determined if eigenfunctions, eigenvalues
The solution for a particle in a one-dimensional box is given by Eq.11.148 as

2 ⎛ nπ x ⎞
ψn = sin ⎜
a ⎝ a ⎟⎠

The momentum operator px is given in Table 11.1 as,

∂
−i˜
∂x
As stated in problem 11.17, if the operation returns the original function multiplied by a constant, the function is an eigenfunction.

∂ψ n
= −i˜
∂x
∂ ⎛ 2 ⎛ nπ x ⎞ ⎞
= −i˜ ⎜⎜ sin ⎜ ⎟⎟
∂x ⎝ a ⎝ a ⎠ ⎟⎠
2 ∂ ⎛ ⎛ nπ x ⎞ ⎞
= −i˜ sin ⎜ ⎟
a ∂x ⎜⎝ ⎝ a ⎠ ⎟⎠
2 ⎛ nπ ⎞ ⎛ nπ x ⎞
= −i˜ ⎜ ⎟ cos ⎜ ⎟
a⎝ a ⎠ ⎝ a ⎠

Since the result is not a constant multiplied by ψ n , ψ n is not an eigenfunction of the momentum operator. This conclusion is related to the
Heisenberg uncertainty principle; the position and momentum operators do no commute, there are no common eigenfunctions, and the two
properties cannot be measured simultaneously and precisely. However, the eigenfunction ψ n , like any other function, can be expressed as
a linear combination of the set of momentum eigenfunctions (compare Eq. 11.117 to Eq. 11.120). The physical significance of this is that

11-60
Chapter 11: Quantum Mechanics and Atomic Structure Solutions

the function ψ n corresponds to the wave train of particular momentum being reflected at the walls of the box and giving rise to a wave train
in the opposite direction.

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11-61
Chapter 11: Quantum Mechanics and Atomic Structure Solutions

*11.29. Treat the three-dimensional particle in a box of sides a, b, and c by analogy with the treatment in Section 11.6. Assume the potential
to be zero inside the box and infinite outside, and proceed by the following steps:
a. Write the basic differential equation that must be solved for the three-dimensional problem.
b. Separate the equation from (a) into terms involving X(x), Y( y), and Z(z).
c. Determine the expressions for X, Y, and Z.
d. Obtain the expression (Eq. 11.150) for the total energy.
Solution:
Given: three-dimensional particle in a box
Required: see above
a. The basic differential equation that must be solved is a three-dimensional form of the Schrodinger, Eq. 11.86.
Ĥψ = Eψ

From Table 11.1 we get,

˜2 2
− ∇ ψ + E p ( x, y, z )ψ = Eψ
2m
Notice that this is analogous to Eq. 11.85

b. The potential energy, E p can be set to zero inside the box, and using the definition for the Del-squared or Laplacian operator, Eq. 11.81,
we get,
∂2 ∂2 ∂2
∇ = 2+ 2+ 2
2

∂x ∂y ∂z
˜ 2 ⎛ ∂2 ∂2 ∂2 ⎞
− ⎜ + + ⎟ψ = Eψ
2m ⎝ ∂x 2 ∂y 2 ∂z 2 ⎠
∂ 2ψ ∂ 2ψ ∂ 2ψ 2mE
+ 2 + 2 =− 2 ψ
∂x 2
∂y ∂z ˜

The energy, E, is separated into its component parts,

E = Ex + E y + Ez

11-62
Chapter 11: Quantum Mechanics and Atomic Structure Solutions

And the wave function is factored as,

ψ = X ( x)Y ( y ) Z ( z )

Substitution of the factored wave function gives,

∂ 2 XYZ ∂ 2 XYZ ∂ 2 XYZ ⎛ 2mEx 2mE y 2mEz ⎞

+ + = ⎜− 2 − 2 − 2 ⎟ XYZ
∂x 2 ∂y 2 ∂z 2 ⎝ ˜ ˜ ˜ ⎠

Dividing by XYZ to eliminate the wave function from the right hand side of the equation gives,

1 ∂ 2 XYZ 1 ∂ 2 XYZ 1 ∂ 2 XYZ 2mE 2mE 2mE

+ + =− 2 x − 2 y − 2 z
XYZ ∂x 2
XYZ ∂y 2
XYZ ∂z 2
˜ ˜ ˜

c. Solving the first term we get

1 ∂ 2 XYZ 1 ∂ ⎛ ∂XYZ ⎞
= ⎜ ⎟
XYZ ∂x 2
XYZ ∂x ⎝ ∂x ⎠
1 ∂ 2 XYZ 1 ∂ ⎛ ∂X ⎞
= ⎜ YZ ⎟
XYZ ∂x 2
XYZ ∂x ⎝ ∂x ⎠
1 ∂ 2 XYZ 1 ∂2 X
= YZ
XYZ ∂x 2 XYZ ∂x 2
1 ∂ 2 XYZ 1 ∂ 2 X
=
XYZ ∂x 2 X ∂x 2
Therefore,

1 ∂2 X 2mE
=− 2 x
X ∂x 2
˜
Similarly, we get

11-63
Chapter 11: Quantum Mechanics and Atomic Structure Solutions

1 ∂ 2Y 2mE
=− 2 y
Y ∂x 2
˜
1 ∂ Z
2
2mE
=− 2 z
Z ∂x 2
˜
d. The total energy is given by Eq. 11.150 as
h 2 ⎛ n12 n22 n32 ⎞
E= + +
8m ⎜⎝ a 2 b 2 c 2 ⎟⎠

This becomes
2 2
nx2 h 2 n y h nz2 h 2
E = E x + E y + Ez = + +
8ma 2 8mb 2 8mc 2
If a = b = c , then

h2
E=
8ma 2
( nx2 + ny2 + nz2 )

Back to Problem 11.29 Back to Top

11-64
Chapter 11: Quantum Mechanics and Atomic Structure Solutions

11.30. What is the quantum-mechanical probability of finding the particle in a one-dimensional “box” in the middle third of the “box”?
Derive an expression that shows how this quantity depends on the quantum number n.
Solution:
Given: one-dimensional box
Required: probability
The quantum mechanical probability is given by

P = ∫ψ *ψ dτ

Since we are trying to find the particle in the middle third of the box, we consider the region between the first third and the second third of
the box. If the box is of length a, then we have the boundaries a / 3 and 2a / 3 .

We use the wave function in the form of Eq. 11.148 to solve.

2
2 a /3⎛ 2 ⎛ nπ x ⎞ ⎞
P = ∫ ⎜⎜ sin ⎜ ⎟ ⎟⎟ dx
a /3
⎝ a ⎝ a ⎠⎠
2 2 a /3 ⎛ nπ x ⎞
P = ∫ sin 2 ⎜ ⎟ dx
a a /3
⎝ a ⎠

1
Using the fact that sin 2 bx = (1 − cos 2bx ) , we continue to solve.
2

11-65
Chapter 11: Quantum Mechanics and Atomic Structure Solutions

2 2 a /3 1 ⎛ ⎛ 2nπ x ⎞ ⎞
P=
a ∫a /3 2⎝⎜ 1 − cos ⎜
⎝ a ⎠⎠
⎟ ⎟ dx

1 2 a /3 ⎛ 2nπ x ⎞
P=
a ∫a /3
1 − cos ⎜
⎝ a ⎠
⎟ dx
2 a /3
1⎡ a ⎛ 2nπ x ⎞ ⎤
P = ⎢x − sin ⎜ ⎟⎥
a⎣ 2nπ ⎝ a ⎠ ⎦ a /3
1 ⎡ 2a a a ⎛ 4anπ ⎞ a ⎛ 2anπ ⎞⎤
P= ⎢ − − sin ⎜ ⎟+ sin ⎜ ⎟⎥
a ⎣ 3 3 2nπ ⎝ 3a ⎠ 2nπ ⎝ 3a ⎠⎦
1 ⎡a a ⎛ 4nπ ⎞ a ⎛ 2nπ ⎞ ⎤
P= ⎢ − sin ⎜ ⎟+ sin ⎜ ⎟⎥
a ⎣ 3 2nπ ⎝ 3 ⎠ 2nπ ⎝ 3 ⎠⎦
1 1 ⎡ ⎛ 4nπ ⎞ ⎛ 2nπ ⎞ ⎤
P= − ⎢sin ⎜ 3 ⎟ − sin ⎜ ⎟⎥
3 2nπ ⎣ ⎝ ⎠ ⎝ 3 ⎠⎦

Back to Problem 11.30 Back to Top

11-66
Chapter 11: Quantum Mechanics and Atomic Structure Solutions

11.31. The classical probability for finding a particle in the region x to x + dx in a one-dimensional box of length a is dx/a.
a. Derive the classical probability for finding the particle in the middle third of the box.
b. Show that as n → ∞, the quantum probability obtained in the previous problem becomes identical to the classical result.
Solution:
Given: box of length a, Pone dimension = dx/a
Required: P, proof
a. We use a similar approach as problem 11.30 to obtain the classical probability for finding the particle in the middle third of the box.
Since the classical probability of finding a particle in the region x to x + dx in a one-dimensional box of length a is dx/a, then the probability
for finding the particle in the middle third of the box is calculated from the integral between a / 3 and 2a / 3 .
2 a /3 dx
Pclassical = ∫
a /3 a
2 a /3
x
Pclassical =
a a /3
1 ⎛ 2a a ⎞
Pclassical = ⎜ − ⎟
a⎝ 3 3⎠
1⎛a⎞
Pclassical = ⎜ ⎟
a⎝3⎠
1
Pclassical =
3

b. The result obtained in the previous problem is

1 1 ⎡ ⎛ 4nπ ⎞ ⎛ 2nπ ⎞ ⎤
P= − ⎢ sin ⎜ ⎟ − sin ⎜ ⎟⎥
3 2nπ ⎣ ⎝ 3 ⎠ ⎝ 3 ⎠⎦

Since n can only be an integer, the quantity in the square brackets in the solution can only have three values.

11-67
Chapter 11: Quantum Mechanics and Atomic Structure Solutions

⎡ ⎛ 4nπ ⎞ ⎛ 2nπ ⎞⎤
⎢sin ⎜ 3 ⎟ − sin ⎜ ⎟⎥ =0 if n = 3, 6,9 …
⎣ ⎝ ⎠ ⎝ 3 ⎠⎦
= − 3 if n = 1, 4, 7 …
= 3 if n = 2,5,8…

1
Therefore, we determine that as n → ∞, the second term will vanish, since we multiply the square bracket by . This yields a result
2nπ
identical to the classical probability above.

1 1 ⎡ ⎛ 4nπ ⎞ ⎛ 2nπ ⎞ ⎤
Pquantum = − sin ⎜ ⎟ − sin ⎜ ⎟⎥
3 2nπ ⎢⎣ ⎝ 3 ⎠ ⎝ 3 ⎠⎦
1
Pquantum = Pclassical =
3

Back to Problem 11.31 Back to Top

11-68
Chapter 11: Quantum Mechanics and Atomic Structure Solutions

*11.32. Problem 11.25 is concerned with the calculation of the minimum energy for an electron confined in a cube. Another approach to the
problem is to consider, on the basis of the uncertainty principle (Eq. 11.60), the uncertainty in the energy if the uncertainty in the
position is equal to the length of the side of the cube. Calculate ΔE for a cube of sides equal to
a. 10 pm and
b. 1 fm (10–15 m),
and compare the results with the minimum energies found for Problem 11.25.
Solution:
Given: electron in a box, a = 10 pm, a = 1 fm, Eq. 11.60
Required: ΔE , compare the results with the Problem 11.25
The uncertainty principle is given as Eq. 11.60,

1
Δq Δp ≥ ˜
2

p2 h
Since E = and ˜ = , we use rearrange Eq. 11.60 to obtain an expression for ΔE .
2m 2π

1 ⎛ h ⎞
Δp = ⎜ ⎟
2Δq ⎝ 2π ⎠
h
Δp =
4πΔq
2
⎛ h ⎞ 1
ΔE = ⎜ ⎟
⎝ 4πΔq ⎠ 2m
h2
ΔE =
32π 2 m ( Δq )
2

c.

11-69
Chapter 11: Quantum Mechanics and Atomic Structure Solutions

a = 10 × 10−12 m
a = 1.0 × 10−11 m

( 6.626 ×10 )
2
−34
Js
ΔE =
( )( )
2
32π 2 9.11× 10−31 kg 1.0 × 10−11 m
ΔE = 1.525 930 53 × 10−17 J
E = 1.5 × 10−17 J

In eV,

1.525 930 53 ×10−17 J

ΔE =
1.602 × 10−19 J eV −1
ΔE = 95.251 593 67 eV
ΔE = 95 eV

d.
a = 1×10−15 m

( 6.626 ×10 )
2
−34
Js
ΔE =
( )( )
2
32π 2 9.11× 10−31 kg 1× 10−15 m
ΔE = 1.525 930 531×10−9 J
ΔE = 1.5 × 10−9 J
1.525 930 531× 10−9 J
ΔE =
1.602 ×10−19 J eV −1
ΔE = 9 525159 367 eV
ΔE = 9.5 ×109 eV

These uncertainties are considerably smaller than the energies calculated for the particle in a box. If we compare the expression for E used
in problem 11.25 to the one used for ΔE , we find that they are smaller by a factor of,

11-70
Chapter 11: Quantum Mechanics and Atomic Structure Solutions

E ⎛ 3h 2 ⎞ ⎛ h2 ⎞
=⎜ ⎟ ÷ ⎜ ⎟
ΔE ⎝ 8ma 2 ⎠ ⎜⎝ 32π 2 m ( Δq )2 ⎟⎠

⎞ ⎛ 32π 2 m ( Δq ) ⎞
2
E ⎛ 3 h2
=⎜ ⎟⎟ × ⎜ ⎟
ΔE ⎜⎝ 8 m a 2 ⎠ ⎜⎝
⎜ h2 ⎟⎟
⎠
E
=12π 2 = 118.435 252 8
ΔE

Back to Problem 11.32 Back to Top

11-71
Chapter 11: Quantum Mechanics and Atomic Structure Solutions

*11.33. Prove that any two wave functions for a particle in a one-dimensional box of length a are orthogonal to each other; that is, they
obey the relationship
a
∫ψψ
0 m n dx = 0, m ≠ n

Solution:
Given: one-dimensional box of length a, two wave functions
Required: proof
To solve this problem, we take the wave functions for levels m and n in the form of Eq. 11. 148,

2 ⎛ mπ x ⎞ 2 ⎛ nπ x ⎞
ψm = sin ⎜ ⎟ and ψ n = a sin ⎜⎝ a ⎟⎠
a ⎝ a ⎠

πx
Substituting y = simplifies the problem. Therefore
a

dy π
=
dx a
a
dx = dy
π
And the boundaries become,

π ( 0)
x = 0; y = =0
a

x = a; y =
π a ( ) =π
a

Solving the integral, we get

11-72
Chapter 11: Quantum Mechanics and Atomic Structure Solutions

π
∫0
ψ mψ n dy
π 2 2
∫0 π
sin my
π
sin ny dy

2 π

π∫
sin my sin ny dy
0

The integral ∫ sin my sin ny dy is a standard integral with the solution

1 ⎡ sin ( m − n ) y sin ( m + n ) y ⎤
∫ sin my sin ny dy = 2 ⎢⎣ m−n
−
m+n
⎥
⎦

Therefore we get,
π
π 2 1 ⎡ sin ( m − n ) y sin ( m + n ) y ⎤
∫0
sin my sin ny dy = ⎢
π 2 ⎣ m−n
−
m+n
⎥
⎦0
π 1 ⎡ sin ( m − n ) π sin ( m + n ) π sin ( m − n ) 0 sin ( m + n ) 0 ⎤
∫0
sin my sin ny dy = ⎢
π ⎢⎣ m−n
−
m+n
−
m−n
+
m+n
⎥
⎥⎦
π 1
∫ sin my sin ny dy = [ 0]
0 π
π
∫0
sin my sin ny dy = 0

As we can see, at the lower limit, both terms are zero since sin 0 = 0 . At the upper limit, both terms are also zero since m and n are integers,
and any sine of any integer of π will return 0.

Therefore the integral is zero and the wave functions ψ m and ψ n are orthogonal.

Back to Problem 11.33 Back to Top

11-73
Chapter 11: Quantum Mechanics and Atomic Structure Solutions

11.34. Use the trial function Ψ = x(a – x) and Eq. 11.247 to calculate an energy for a particle in a one-dimensional box of length a.
Solution:
Given: Ψ, Eq. 11.247, one-dimensional box of length a
Required: E
Energy is given by Eq. 11.247 as,

E=
∫ψ * Hˆψ dτ
∫ψ *ψ dτ
The Ĥ operator is given in Table 11.1 as,

˜2 2 ˆ
− ∇ + Ep
2m

The potential energy, E p can be set to zero inside the box, and the Del-squared or Laplacian operator, is given by Eq. 11.81

∂2 ∂2 ∂2
∇ = 2+ 2+ 2
2

∂x ∂y ∂z

For a one-dimensional box,

d2
∇ = 2
2

dx

h
Using ˜ = , and the boundaries of the box as 0 and a, we rewrite Eq. 11.247 as
2π

11-74
Chapter 11: Quantum Mechanics and Atomic Structure Solutions

a ⎛ ˜ 2 d 2Ψ ⎞
∫
0
Ψ⎜−
⎝ 2m dx
2 ⎟ dx
⎠
E= a
∫0
Ψ 2 dx

h2 a ⎛ d 2 ( x ( a − x )) ⎞
− 2 ∫ x (a − x)⎜ ⎟⎟ dx
8π m 0 ⎜ dx 2
E= ⎝ ⎠
a
∫ x 2 ( a − x ) dx
2
0

Solving the denominator and numerator separately provides a much easier way to obtain the result.

The numerator is,

11-75
Chapter 11: Quantum Mechanics and Atomic Structure Solutions

h2 a ⎛ d 2 ( x ( a − x )) ⎞
( )⎜
8π 2 m ∫0
− x a − x ⎜ ⎟ dx
dx 2 ⎟
⎝ ⎠
h2 a ⎛ d ( ax − x ) ⎞
2 2

= − 2 ∫ x (a − x)⎜ ⎟ dx
8π m 0 ⎜ dx 2 ⎟
⎝ ⎠
h2 a ⎛ d ( a − 2x) ⎞
= − 2 ∫ x (a − x)⎜ ⎟ dx
8π m 0 ⎝ dx ⎠
h2 a
x ( a − x )( −2 ) dx
m∫
=−
8π 02

h2
= 2 ∫ ( ax − x 2 ) dx
a

4π m 0

a
h 2 ⎡ ax 2 x 3 ⎤
= 2 ⎢ − ⎥
4π m ⎣ 2 3 ⎦0

h2 ⎡ a ( a ) ( a ) ⎤
2 3

= 2 ⎢ − − 0⎥
4π m ⎣⎢ 2 3 ⎥⎦
h2 ⎡ a3 a3 ⎤
= 2 ⎢ − ⎥
4π m ⎣ 2 3 ⎦
a3h2
=
24π 2 m

The denominator is,

11-76
Chapter 11: Quantum Mechanics and Atomic Structure Solutions

a
∫ x 2 ( a − x ) dx
2
0

= ∫ x 2 ( a 2 − 2ax + x 2 ) dx
a

= ∫ ( a 2 x 2 − 2ax 3 + x 4 ) dx
a

0
a
⎡ 2 x3 x 4 x5 ⎤
= ⎢a −a + ⎥
⎣ 3 2 5 ⎦0
⎡ 2 ⎛ a3 ⎞ ⎛ a 4 ⎞ ⎛ a5 ⎞ ⎤
= ⎢a ⎜ ⎟ − a ⎜ ⎟ + ⎜ ⎟ − 0⎥
⎣ ⎝ 3⎠ ⎝ 2 ⎠ ⎝ 5 ⎠ ⎦
a5 a5 a5
= − +
3 2 5

⎛1 1 1⎞
= a5 ⎜ − + ⎟
⎝3 2 5⎠
a5
=
30

Therefore E is,

a3h2 a5
E= ÷
24π 2 m 30
a 3 h 2 30
E= ×
24π 2 m a 5
30h 2
E=
3 × 8π 2 ma 3
10 ⎛ h 2 ⎞
E= 2⎜ ⎟
π ⎝ 8ma 3 ⎠
5h 2
E=
4π 2 ma 2

11-77
Chapter 11: Quantum Mechanics and Atomic Structure Solutions

Notice that for n = 1, the exact energy is

h2
8ma 3

And that in this case we have

10
times the exact energy.
π2

Back to Problem 11.34 Back to Top

11-78
Chapter 11: Quantum Mechanics and Atomic Structure Solutions

11.35. a. At a node, a wave function passes through zero. For the problem of the particle in a box, how many nodes are there for n = 2 and
n = 3?
b. From the expression for the radial function for the 3s electron (Table 11.4), obtain expressions for the position of the radial nodes
(i.e., the nodes in the solution of the radial equation) in terms of Z and a0.
Solution:
Given: particle in a box, n = 2 and n = 3, 3s electron, Table 11.4
Required: number of nodes, position of nodes in terms of Z and a0 (r)
a. For n = 2, there is one node. For n = 3, there are two nodes. We do not count the points x = 0 and x = a, where the wave function
becomes zero but does not pass through it.
b. From Table 11.4, we have the radial function for the 3s electron is,
3/ 2
1 ⎛Z⎞ ⎛ 4Zr 4Z 2 r 2 ⎞ – Zr/3a0
R30 = 6 – + e
9 3 ⎜⎝ a0 ⎟⎠ ⎜⎝ a
0 9a 2 ⎟⎠
0

Since we know the nodes are at a position where the wave function passes through zero, we set the expression equal to zero to solve for r.
3/ 2
1 ⎛Z⎞ ⎛ 4Zr 4Z 2 r 2 ⎞ – Zr /3a0
R30 = ⎜ ⎟ ⎜ 6 − + ⎟e =0
9 3 ⎝ a0 ⎠ ⎝ a0 9a02 ⎠
3/2
1 ⎛Z⎞ ⎛ 4 Zr 4Z 2 r 2 ⎞ – Zr /3a0
⎜ ⎟ ⎜ 6 − + ⎟e =0
9 3 ⎝ a0 ⎠ ⎝ a0 9a02 ⎠
4 Zr 4Z 2 r 2
6− + =0
a0 9a02
4Z 2 2
6 a02 − 4 Za0 r + r =0
9
We can solve for r using the quadratic equation.

11-79
Chapter 11: Quantum Mechanics and Atomic Structure Solutions

−b ± b 2 − 4ac
r± =
2a
1 ⎛ ⎛ 4Z 2 ⎞ ⎞
r± =
⎛ 4Z 2 ⎞ ⎜
⎜ 4 Za 0 ± ( 4 Za 0 )
2
− 4 ⎜
9 ⎠
⎟ ( 6 a0
2
) ⎟
⎟
⎝
2⎜ ⎟⎝ ⎠
⎝ 9 ⎠
1 ⎛ 32Z 2 a02 ⎞
r± = ⎜ 4 Za ± 16 Z 2
a 2
− ⎟
⎛ 8Z 2 ⎞ ⎜⎝ ⎟
0 0
3 ⎠
⎜ ⎟
⎝ 9 ⎠

9 ⎛ 32 ⎞
r± = 2 ⎜
⎜ 4 Za0 ± 16 − Za0 ⎟⎟
8Z ⎝ 3 ⎠
9 ⎛ 16 ⎞
r± = 2 ⎜⎜ 4 Za0 ± Za0 ⎟⎟
8Z ⎝ 3 ⎠
9 ⎛ 4 ⎞
r± = 2 ⎜ 4 Za0 ± Za0 ⎟
8Z ⎜⎝ 3 ⎟
⎠
9 a0 ⎛ 1 ⎞
r± = ⎜⎜1 ± ⎟
2Z⎝ 3 ⎟⎠

r± =
3 a0
2Z
(
3± 3 )
Therefore the two radial nodes are located at distances of r =
2 Z
(
3 a0
3+ 3 ) and r = 32 aZ (3 − 3 ) from the nucleus.
0

Back to Problem 11.35 Back to Top

11-80
Chapter 11: Quantum Mechanics and Atomic Structure Solutions

11.36. The vibration frequency of the N2 molecule corresponds to a wave number of 2360 cm–1. Calculate the zero-point energy and the
energy corresponding to v = 1.
Solution:

Given: N2, ν = 2360 cm –1 , ν = 1

Required: Zero-point energy

The zero-point energy at ν = 1 can be calculated using,

3
E= hν 0
2

Frequency, ν 0 , is calculated from, Eq. 11.1,

c = λν
1
ν =
λ
c
ν= = cν
λ
3
E= hcν
2
3
( )(
E = 6.626 ×10−34 J s 2.998 × 1010 cm s −1
2
) ( 2360 cm )
–1

E = 7.032 120 79 × 10−20 J

E = 7.032 × 10−20 J

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11-81
Chapter 11: Quantum Mechanics and Atomic Structure Solutions

*11.37. If a rigid body rotates in the XY plane, about the Z axis, the angular momentum operator is

∂
Lˆ = – i ˜
∂φ

(see Figure 11.15). If the moment of inertia is I, what is the energy operator?
(For additional problems dealing with molecular vibrations and rotations, see Chapter 13.)
Solution:
Given: the angular momentum operator, I
Required: energy operator
The energy is related to the angular momentum by Eq. 11.215,

L2
E = Ek =
2I
The energy, or Hamiltonian operator is therefore,
2
1 ⎛ ∂ ⎞
E= ⎜ −i ˜ ⎟
2I ⎝ ∂φ ⎠
1 ⎛ 2 2 2 ∂
2
⎞
E= ⎜ ( −1) i ˜ 2 ⎟
2I ⎝ ∂φ ⎠
−˜ 2 ∂ 2
E=
2 I ∂φ 2
h
˜=
2π
−h2 ∂ 2
E=
8π 2 I ∂φ 2

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11-82
Chapter 11: Quantum Mechanics and Atomic Structure Solutions

11.38. Calculate the ionization energy of the hydrogen atom on the basis of the Bohr theory.
Solution:
Given: hydrogen atom
Required: ionization energy

The energy required to remove the electron from the lowest energy level in hydrogen ( n1 = 1) to infinity, ( n2 = ∞ ) is the ionization energy.
We use Eq. 11.50, Eq. 11.1 and the expression for energy, E = hν , to solve.

1 ⎛ 1 1 ⎞
ν = = R⎜ 2 − 2 ⎟
λ ⎝ n1 n2 ⎠
c = λν
c
ν= = cν
λ
⎛ 1 1 ⎞
E = hcR ⎜ 2 − 2 ⎟
⎝ n1 n2 ⎠

) ( 2.998 ×10 ) (1.0968 ×10 ) ⎛1 1 ⎞

(
E = 6.626 × 10−34 J s 8
m s −1 7
m −1 ⎜ 2 − 2 ⎟
⎝1 ∞ ⎠
E = 2.178 765 56 × 10−18 J
E = 2.179 × 10−18 J

In eV,

2.178 765 56 ×10−18 J

E=
1.602 × 10−19 J eV −1
E = 13.600 284 4 eV
E = 13.60 eV

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11-83
Chapter 11: Quantum Mechanics and Atomic Structure Solutions

11.39. Calculate, on the basis of the Bohr theory, the linear velocity of an electron (mass = 9.11 × 10–31 kg) in the ground state of the
hydrogen atom. To what de Broglie wavelength does this velocity correspond? Deduce an equation for the de Broglie wavelength, in
a Bohr orbit of quantum number n, with Z = 1, in terms of a0 and n. What is the ratio of the circumference of a Bohr orbit of
quantum number n to the de Broglie wavelength?
Solution:

Given: m = 9.11× 10 –31 kg, n, Z = 1

Required: u , λde Broglie , λde Broglie ( expression ) , C : λde Broglie ( expression )

Velocity is given in Eq. 11.39 as,

h
L = mur = n = n= (n = 0,1, 2, …)
2π
Since we are told the electron is in the ground state of the hydrogen atom, n = 1 and velocity is therefore,

h
u=
2π mr

From Eq. 11. 44, we take r = a0 . This is because a0 is a length and is the radius of the orbit for n = 1 for the hydrogen atom itself (Z = 1).
The length a0 is known as the Bohr radius and has a value of 52.92 pm (1 picometre = 10–12 m).

u=
( 6.626 ×10 J s ) −34

2π ( 9.11×10 kg )( 52.92 × 10
−31 −12
m)
u = 2 187 425.903 m s −1
u = 2.19 × 106 m s −1

The de Broglie wavelength is given by Eq. 11.56,

h h
λ= =
p mu

11-84
Chapter 11: Quantum Mechanics and Atomic Structure Solutions

Solving, using the velocity determined above we get,

λ=
( 6.626 ×10 J s )
−34

( 9.11×10 kg )( 2 187 425.903 m s )

−31 −1

λ = 3.325 061 66 ×10−10 m

λ = 3.33 ×10−10 m = 333 pm

To find the de Broglie expression for wavelength in terms of a0 and n we use Eq. 11.56 and Eq. 11.39.

nh
u=
2π mr
2π r h
=
n mu
h 2π r
λ= =
mu n
From Eq. 11. 43 with Z = 1,

n2
r= a0
Z
r = a0 n 2
2π
λ=
n
( a0 n2 )
λ = 2π a0 n

The expression for circumference is C = 2π r , hence

C = 2π n 2 a0 and the ratio C : λ is

11-85
Chapter 11: Quantum Mechanics and Atomic Structure Solutions

2π a0 n 2
C :λ =
2π a0 n
C :λ = n

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11-86
Chapter 11: Quantum Mechanics and Atomic Structure Solutions

11.40. For a hydrogen-like atom (a one-electron system with a charge number of Z), find the radius of the sphere on which the probability of
finding the 1s electron is a maximum. Compare the result to the expression of Eq. 11.44.
Solution:
Given: a one-electron system, charge of Z
Required: r
The radius of the sphere of maximum probability corresponds to the maximum in the radial probability function, given in Section 11.8 by

4π r 2ψ 12s

We find the maximum r by differentiating the radial probability function with respect to r and setting it equal to zero.
Using Eq. 11.193, and Z, we solve to obtain r.

11-87
Chapter 11: Quantum Mechanics and Atomic Structure Solutions

e –2r / a0
ψ =
2
1s
π a03
3
⎛ 1 ⎞⎛ Z ⎞
P = 4 π r ⎜ ⎟ ⎜ ⎟ e –2Zr / a0
2

⎝ π ⎠ ⎝ a0 ⎠
dP d ⎛ ⎞
3
2⎛ Z ⎞
= ⎜ 4π r ⎜ ⎟ e –2Zr / a0 ⎟ = 0
dr dr ⎜ ⎝ a0 ⎠ ⎟
⎝ ⎠
3 3
⎛Z⎞ ⎛ Z ⎞ ⎛ −2Z ⎞ –2Zr / a0
8π r ⎜ ⎟ e –2Zr / a0 + 4π r 2 ⎜ ⎟ ⎜ ⎟e =0
a
⎝ 0⎠ a a
⎝ 0⎠ ⎝ 0 ⎠
3
⎛Z⎞ ⎛ ⎛ Z ⎞⎞
8π ⎜ ⎟ e –2Zr / a0 ⎜⎜ r ⎜ 1 − r ⎟ ⎟⎟ = 0
⎝ a0 ⎠ ⎝ ⎝ a0 ⎠ ⎠
⎛ Z⎞
r ⎜1 − r ⎟ = 0
⎝ a0 ⎠
Z
r = 0, 1 − r = 0
a0
a0
r=
Z

We ignore the r = 0 value since it does not make sense for the radius to be zero. The expression for r obtained here is identical to Eq. 11.43
for the case of a 1s electron.

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11-88
Chapter 11: Quantum Mechanics and Atomic Structure Solutions

*11.41. Calculate the reduced masses of the hydrogen and deuterium atoms, using the following masses for the particles:

Electron: 9.1095 × 10–31 kg

Proton: 1.6727 × 10–27 kg
Deuterium nucleus: 3.3434 × 10–27 kg

a. Explain qualitatively what effect the different reduced masses will have on the Bohr radii and therefore on the positions of the
lines in the atomic spectra.
b. The Balmer spectrum of hydrogen has a line of wavelength 656.47 nm. Deduce the wavelength of the corresponding line in the
spectrum of deuterium.
Solution:
Given: particle masses above, λ = 656.47 nm

Required: μ , a, b,

The reduced mass is calculated from Eq. 11.152,

m1m2
μ=
m1 + m2

For hydrogen we get,

11-89
Chapter 11: Quantum Mechanics and Atomic Structure Solutions

μH =
( me mH )
me + mH

μH =
( 9.1095 ×10 –31
kg )(1.6727 × 10 –27 kg )
9.1095 ×10 –31 kg + 1.6727 × 10 –27 kg
μH = 9.104 54 ×10 –31 kg
μH = 9.1045 ×10 –31 kg

μD =
( me mD )
me + mD

μD =
( 9.1095 ×10 –31
kg )( 3.3434 ×10 –27 kg )
9.1095 ×10 –31 kg + 3.3434 ×10 –27 kg
μD = 9.10702 ×10 –31 kg
μD = 9.1070 ×10 –31 kg

a. The reduced mass and the Bohr radius are related by Eq. 11.44,
h 2 ∈0
a0 =
πμ e2

The Bohr radius is inversely proportional to the reduced mass, therefore it is slightly smaller for deuterium than it is for hydrogen.
Additionally, the Bohr radius is inversely proportional to the energies. Therefore, the energies are slightly greater for deuterium than it is for
hydrogen. The frequencies of the transitions are therefore slightly greater for deuterium, and the wavelengths are slightly shorter.
b. The wavelengths are in the inverse ratio of the reduced masses, and therefore we have the ratio,
λH 9.1045
=
λD 9.1070

The wavelength of the line in the spectrum of deuterium is therefore,

11-90
Chapter 11: Quantum Mechanics and Atomic Structure Solutions

9.1045
λ= × 656.47 nm
9.1070
λ = 656.289 789 7 nm
λ = 656.29 nm

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11-91
Chapter 11: Quantum Mechanics and Atomic Structure Solutions

11.42. Calculate the wavelength and energy corresponding to the n = 4 to n = 5 transition in the hydrogen atom.
Solution:
Given: n = 4, n = 5, hydrogen atom
Required: λ , E

From Eq. 11.50, we can calculate the wavelength,

1 ⎛ 1 1 ⎞
v = = R⎜ 2 − 2 ⎟
λ ⎝ n1 n2 ⎠
−1
⎛ ⎛ 1 1 ⎞⎞
λ = ⎜⎜ R ⎜ 2 − 2 ⎟ ⎟⎟
⎝ ⎝ n1 n2 ⎠ ⎠
−1
⎛ ⎛ 1 1 ⎞⎞
λ = ⎜1.0968 ×107 m −1 ⎜ 2 − 2 ⎟ ⎟
⎝ ⎝ 4 5 ⎠⎠
λ = 4.05219 ×10−6 m
λ = 4.0522 ×10−6 m

Energy is determined from Eq. 11.1 and E = hν ,

E = hν
c = λν
hc
E=
λ
( 6.626 ×10 −34
Js ) ( 2.998 ×10 8
m s −1 )
E= −6
4.05219 ×10 m
−20
E = 4.902 22 × 10 J
E = 4.902 × 10−20 J

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11-92
Chapter 11: Quantum Mechanics and Atomic Structure Solutions

11.43. Calculate, in joules and in atomic units, the potential energy of an electron in the n = 2 orbit of the hydrogen atom.
Solution:
Given: n = 2, hydrogen atom
Required: Ep
We use Eq. 11.48, with Z = 1 for a hydrogen atom to solve for Ep,

Z 2e2
Ep = −
4π ∈0 n 2 a0

(1.602 ×10 C)
−19 2

Ep = −
4π ( 8.854 × 10−12 C2 N −1 m −2 ) 22 ( 52.92 × 10−12 m )
E p = −1.089 67 ×10−18 J
E p = −1.090 ×10−18 J

e2
In atomic units of ,
4π ∈0 a0

12
Ep = −
22
E p = −0.25 au

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11-93
Chapter 11: Quantum Mechanics and Atomic Structure Solutions

11.44. The first ionization energy of the Li atom is 5.39 eV. Estimate an effective nuclear charge Zeff for the valence electron in the Li
atom.
Solution:

Given: Eionization = 5.39 eV

Required: Zeff
Problems 11.44 and 11.45 are conveniently worked out with reference to Problem 11.38, where we deter. emied the ionization energy for
hydrogen as 13.60 eV. From Eq. 11.49,

Z 2e2
E = Ek + E p = −
8π ∈0 n 2 a0
2
Z eff
the first ionization energy is proportional to .
n2
For H, Zeff = 1 and n = 1, hence,

⎛ Z2 ⎞
I = 13.60 eV ⎜ eff2 ⎟
⎝ n ⎠
⎛ 12 ⎞
I = 13.60 eV ⎜ 2 ⎟
⎝1 ⎠
I = 13.60 eV
For Li, n = 2, hence,

11-94
Chapter 11: Quantum Mechanics and Atomic Structure Solutions

⎛ Z2 ⎞
I = 13.60 eV ⎜ eff2 ⎟
⎝ n ⎠
n2 I
Z eff =
13.60 eV

Z eff =
(
22 5.39 eV )
13.60 eV
Z eff = 1.259 084 635
Z eff = 1.26

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11-95
Chapter 11: Quantum Mechanics and Atomic Structure Solutions

11.45. The first ionization energy of the Na atom is 5.14 eV. Estimate the effective nuclear charge Zeff for the valence electron in the Na
atom.
Solution:

Given: Eionization = 5.14 eV

Required: Zeff
For Na, n = 3, hence,

⎛ Z2 ⎞
I = 13.60 eV ⎜ eff2 ⎟
⎝ n ⎠
32 I
Z eff =
13.60 eV

Z eff =
(
32 5.14 eV )
13.60 eV
Z eff = 1.844 307 618
Z eff = 1.84

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11-96
Chapter 11: Quantum Mechanics and Atomic Structure Solutions

*11.46. Use Slater’s method (Section 11.13) to determine the effective nuclear charge for
a. a 3s electron in the chlorine atom,
b. a 3p electron in the phosphorus atom, and
c. the 4s electron in the potassium atom.
Solution:
Given: a – c,
Required: Zeff
Using the Slater method, we find Zeff from Eq. 254,

Z eff = Z − σ

We use the four rules to help solve for Zeff.

a. The nuclear charge of Cl is, Z = 17. We then subtract:
0.30 for the other 3s electron
5 × 0.35 for the five 3p electrons
8 × 0.85 for the eight 2s and 2p electrons,
2 × 1.00 for the two 1s electrons
Z eff = 17 − 0.30 − 5 × 0.35 − 8 × 0.85 − 2 ×1.00
Z eff = 6.15

b. The nuclear charge of P is, Z = 15. We then subtract:

2 × 0.30 for the 3s electron
2 × 0.35 for the other 3p electrons
8 × 0.85 for the eight 2s and 2p electrons,
2 × 1.00 for the two 1s electrons
Z eff = 15 − 2 × 0.30 − 2 × 0.35 − 8 × 0.85 − 2 ×1.00
Z eff = 4.9

c. The nuclear charge of K is, Z = 19. We then subtract:

8 × 0.85 for the eight 2s and 2p electrons,

11-97
Chapter 11: Quantum Mechanics and Atomic Structure Solutions

10 ×1.00 for the 1s, 2s and 2p electrons

Z eff = 19 − 8 × 0.85 − 10 ×1.00
Z eff = 2.2

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11-98
Chapter 11: Quantum Mechanics and Atomic Structure Solutions

*11.47. A normalized Slater orbital for the 1s orbital in the helium atom is
3/ 2
1 ⎛ Z eff ⎞
ψ 1s = ⎜ ⎟ exp(– Z eff r/a0 )
π ⎝ a0 ⎠

where Zeff is the effective charge number. It leads to the following expression for the energy

e 2 ⎛ 2 27 ⎞
E= ⎜ Z eff − Z eff ⎟ .
a0 ⎝ 8 ⎠

Treat Zeff as a variation parameter, and calculate a minimum energy in terms of e and a0. Why is the optimum value of Zeff different
from the actual charge number?
Solution:
Given: E
Required: Emin in terms of e and a0, optimum Zeff
To solve we minimize E with respect to Zeff,

dE e 2 ⎛ 27 ⎞
= ⎜ 2 Z eff − ⎟ = 0
dZ eff a0 ⎝ 8 ⎠
e2 ⎛ 27 ⎞
⎜ 2 Z eff − ⎟ = 0
a0 ⎝ 8 ⎠
27
2 Z eff − =0
8
27
Z eff =
16

Solving for Emin in terms of e and a0, we get,

11-99
Chapter 11: Quantum Mechanics and Atomic Structure Solutions

27
Z eff =
16
e 2 ⎛ ⎛ 27 ⎞ 27 ⎛ 27 ⎞ ⎞
2

Emin = ⎜ ⎜ ⎟ − ⎜ ⎟ ⎟⎟
a0 ⎜⎝ ⎝ 16 ⎠ 8 ⎝ 16 ⎠ ⎠
2
⎛ 729 ⎞ e
Emin = − ⎜ ⎟
⎝ 256 ⎠ a0

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11-100
Chapter 11: Quantum Mechanics and Atomic Structure Solutions

*11.48. Use the wave function for the 1s orbital of the hydrogen atom, given in Table 11.5, to obtain an expression for the probability that
the electron lies between the distance r and r + dr from the nucleus. (Use spherical polar coordinates, for which the volume element
is r2 dr sin θ dθ dφ .)

Solution:
Given: Table 11.5
Required: P in spherical polar coordinates
The expression for the wave function for the 1s orbital of the hydrogen atom is given in Table 11.5 as,
3/ 2
1 ⎛ 1⎞
ψ 1s = ψ 100 = e – r / a0
π ⎜⎝ a0 ⎟⎠

To find P, we must solve for,

r + dr 1 –2r / a0
∫r
ψ *ψ =
π a03
e dr

Multiplying by the volume element, integrating θ from 0 to π and φ from 0 to 2π , we convert to spherical polar coordinates.

π 2π 1 –2r / a0 2
∫ ∫
0 0
ψ *ψ =
π a03
e r dr sinθ dθ dφ

separating the integrals,

π π
∫0
sinθ dθ = − cos θ 0
π
∫ sinθ dθ = − ( −1 − 1)
0
π
∫ sinθ dθ = 2
0
π2 π
∫ dφ = φ
2
0 0
π2
∫ dφ = 2π
0

11-101
Chapter 11: Quantum Mechanics and Atomic Structure Solutions

Therefore we get,

1 –2r / a0 2
P =4π e r dr
π a03
4 2 –2r / a0
P= r e dr
a03
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11-102
Chapter 11: Quantum Mechanics and Atomic Structure Solutions

*11.49. Unsöld’s theorem (Section 11.8) states that, for a given value of l, the sum of the values of

∑ [Θ
l ,m
l ,m (θ )Φ m (φ )]2

is independent of θ and φ , i.e., is a constant. Write all these functions for the 2p orbitals (see Tables 11.2 and 11.3), and show that
their sum shows no angular dependence.
Solution:
Given: Unsöld’s theorem, Tables 11.2 and 11.3
Required: functions for the 2p orbitals, show there is no angular dependence in their sum
From Tables 11.2 and 11.3, we have the following for l = 1 and ml = -1, 0, 1.

cos φ 6
Φ1 = Θ10 = cos θ
π 2
1 3
Φ0 = Θ1±1 = sin θ
2π 2
sin φ
Φ −1 =
π
The functions for the 2p orbitals are therefore,

6 1
Θ10 Φ 0 = cos θ
2 2π
3 1
Θ11Φ1 = sin θ cos φ
2 π
3 1
Θ1−1Φ −1 = sin θ sin φ
2 π
The sum of their squares is,

11-103
Chapter 11: Quantum Mechanics and Atomic Structure Solutions

2 2 2
⎛ 6 1 ⎞ ⎛ 3 1 ⎞ ⎛ 3 1 ⎞
= ⎜⎜ cos θ ⎟⎟ + ⎜⎜ sin θ cos φ ⎟⎟ + ⎜⎜ sin θ sin φ ⎟⎟
⎝ 2 2π ⎠ ⎝ 2 π ⎠ ⎝ 2 π ⎠
6 1 3 2 1 3 1
= cos 2 θ + sin θ cos 2 φ + sin 2θ sin 2 φ
4 2π 4 π 4 π
=
4π
3
( )
cos 2 θ + sin 2 θ ( cos 2 φ + sin 2 φ )

cos 2 φ + sin 2 φ = 1

3
=
4π
( cos 2 θ + sin 2 θ )

3
=
4π

This solution is independent of θ and φ .

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11-104