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Homework #1 Solutions:

Chapter 1:

Q1.1.) The energy levels of the hydrogen atom are quantized and the largest energy
corresponds to n Æ ∞. The highest photon energy corresponds to the energy released
when an electron makes a transition to the n = 1 state.

Q1.10.) The divergence between the classical theory and the experimental results is very
pronounced in the ultraviolet region. In particular, because the classical theory predicts
that the spectral density increases as ν2, the total energy radiated by a blackbody is
predicted to be infinite. This prediction was clearly wrong, and the lack of agreement
with the experimental results was viewed by scientists of the time as a catastrophe.

~ ν 1 E
Q1.15.) ν = = =
c λ hc

P1.3.) Note: we realize that the RH constant given in the problem (109,737 cm-1) is
incorrect. The true value is 109,677.581 cm-1. We are not going to count off for having
used the incorrect value.

The highest value for the wavenumber corresponds to 1/n Æ 0. Also, wavenumber = 1/λ
= E/hc. Therefore:

~ 1
ν = R H ( 2 )cm −1 = 109,677cm −1 → E max = 2.17871 × 10 −18 J for Lyman series.
1

~ 1
ν = R H ( 2 )cm −1 = 27,419.3cm −1 → E max = 5.44676 × 10 −19 J for Balmer series.
1

~ 1
ν = R H ( 2 )cm −1 = 12,186.3cm −1 → E max = 2.42078 × 10 −19 J for Paschen series.
1
P1.7.)

Etotal ∞ 8πhν 3 1 hν h
=∫ dν ... And ...x = ∴ dx = dν
V 0 c 3
e hv / kT
−1 kT kT
∞ ∞
8πhν 3 1 8πk 4T 4 x3 8π 5 k 4T 4
∫0 c 3 e hv / kT − 1 dν =
h 3c 3 ∫0 e x − 1 dx =
15h 3 c 3
Etotal 8π 5 (1.381 × 10 − 23 J / K ) 4 × (1350 K ) 4
1350 K → = −34
= 2.51 × 10 −3 J / m 3
V 15 × (6.626 × 10 Js) (2.998 × 10 m / s )
3 8

E
5250 K → total = 0.575 J / m 3
V

p h 6.626 × 10 −34 Js
P1.12) ν = = = = 4.16 × 10 6 m / s
m mλ (9.109 × 10 kg ) × (0.175 × 10 m)
− 31 −9

Etotal 5.25W × 1Js −1W −1


P1.24) n ='
= − 34
= 8.59 × 1018 s −1
E photon 6.626 × 10 Js × 2.998 × 10 m / s
8

325 × 10 −9 m

P1.26)

2.179 × 10 −18 J
En = −
n2
E1 = −2.179 × 10 −18 J
E 2 = −5.448 × 10 −19 J
E3 = −2.421 × 10 −19 J
E 4 = −4.085 × 10 −19 J
E 4 − 4.085 × 10 −19 J = −1.362 × 10 −19 J − 4.085 × 10 −19 J = −5.447 × 10 −19 J

This energy corresponds to the n = 2 state of H.

Chapter 2:

Q2.3). The units of φ are radians. We can rewrite the wavefunction as:

φ φ
ψ ( x, t ) = A sin( k[ x + ] − ωt ) or ψ ( x, t ) = A sin( kx − ω[t − ])
k ω

The first equation suggests a shift in x, and the second suggests a shift in t.
Q2.9). Consider the nodes in the function ψ ( x, t ) = A sin( kx − ωt ) . The wave amplitude
x t
is zero for 2π ( + ) = nπ where n is an integer. Solving for x, we obtain the location
λ T
n t
of the nodes as x = λ ( − ). We see that x decreases as t increases, showing that the
2 T
wave is moving in the direction of negative x. Or ψ ( x, t ) = A sin( kx + ωt ) is acceptable
too.

Q2.11). If the difference in energy between levels becomes small compared to kT, the
levels become “smeared out” and overlap. When this happens, the levels can no longer
be distinguished, and from the viewpoint of the observer, the system has a continuous
energy spectrum.

P2.3).

d 3x
a. = 6 Æ not an eigenfunction
dx 3

∂xy ∂xy
b. x +y = 2 xy Æ Eigenfunction with eigenvalue +2
∂x ∂y

∂2
c. (sin θ cos φ ) = − sin θ cos φ Æ Eigenfunction with eigenvalue -1
∂θ 2

P2.4). Note that your answers to parts (a) and (b) are not identical. As we will learn in
Chapter 18, the fact that switching the order of the operators x and d/dx changes the
outcome of the operation ABf(x) is the basis for the Heisenberg uncertainty principle.

d 2 2 2
a. [ x( xe − ax )] = 2 xe − ax − 2ax 3 e − ax
dx

d 2 2 2
b. x[ ( xe − ax )] = xe − ax − 2ax 3 e − ax
dx
2 2
∂ ∂ (e − a ( x + y ) ) ∂ 2 2 2 2 2 2)
c. y [ x ] = y [−2axye − a ( x + y ) ] = −2ay 2 e − a ( x + y ) + 4a 2 x 2 y 2 e − a ( x + y
∂x ∂y ∂x

P2.10).

2π 2π
1

φ m* (θ )φ n (θ )dθ = ∫ e −imθ e −inθ dθ = ∫ e i ( n − m )θ dθ = [ e i ( n − m )θ ]02π

0
0 0
i ( n − m)

1 1
= [ e i ( n − m ) 2π − e 0 ] = [cos[(n − m)2π ] + i sin[(n − m)2π ] − 1]
i ( n − m) i ( n − m)

Because n and m are integers, (n-m) is an integer and the arguments of the sine and cosine
functions are integral multiples of 2π.


1
∫φ (θ )φ n (θ )dθ = [1 + 0 − 1] = 0
*
m
0
i ( n − m)

P2.12).

d 2 (ae −3 x + be −3ix )
a. 2
= 9ae −3 x − 9be −3ix Æ Not an eigenfunction
dx

d 2 sin 2 x
b. 2
= −2 sin 2 x + 2 cos 2 x Æ Not an eigenfunction
dx

d 2 e −ix
c. = e −ix Æ Eigenfunction with eigenvalue -1
dx 2

d 2 cos ax
d. 2
= −a 2 cos ax Æ Eigenfunction with eigenvalue –a2
dx
2
d 2 e − ix 2 2
e. 2
= −2ie −ix − 4 x 2 e −ix Æ Not an eigenfunction
dx

P2.21).

a. sin θ cos φ = − sin θ sin φ Æ Not an eigenfunction
∂φ

1 1
1 d − 2 x2 − x2
b. e = −e 2 Æ Eigenfunction with eigenvalue -1
x dx

sin θ d
c. sin θ = sin θ Æ Eigenfunction with eigenvalue +1
cos θ dθ

P2.26).

n 2 g2 − (ε 2 − ε 1 )
= exp[ ]
n 1 g1 kT
n2 g (ε − ε 1 )
ln( ) = ln( 2 ) − 2
n1 g1 kT
1 k g n
= [ln( 2 ) − ln( 2 )]
T (ε 2 − ε 1 ) g1 n1
(ε 2 − ε 1 )
T=
g n
k[ln( 2 ) − ln( 2 )]
g1 n1
n2 3.00 × 10 − 21 J
for = 0.225T = = 145 K
n1 1.381 × 10 − 23 J / K × [ln(1) − ln(0.225)]
n2 3.00 × 10 − 21 J
for = 0.875T = − 23
= 1.63 × 10 3 K
n1 × × −
1.381 10 J / K [ln(1) ln(0.875)]

P2.28).

∫φ (θ )φ n (θ )dθ = 1 for m=n


* *
NN m
0

2π 2π
1
∫e ∫ dθ = 2πNN
−inθ inθ
NN *
e dθ = NN * *
= 1 . This is satisfied for N = and the
0 0 2π
1
normalized functions are φ n (θ ) = e inθ → 0 ≤ θ ≤ 2π