Chapter 39

1. We can use the mc2 value for an electron from Table 37-3 (511 ´ 103 eV) and hc =
1240 eV · nm by writing Eq. 39-21 as

F
2h 2 nx2 n y nz2
2
I b g Fn
hc
2 2
n y2 I
nz2
E nx ,ny ,nz = GH
8m Lx Ly Lz
2 JK c h GH L
+ 2 + 2 =
8 mc 2
x
2
x
+
L2y
+ JK
L2z
.

For nx = ny = nz = 1, we obtain

(1240eV × nm ) æ ö
2
1 1 1
E1,1 = ç + + ÷ = 3.21 eV.
8 ( 511´10 eV ) çè ( 0.800nm ) (1.600nm ) ( 0.390nm ) ÷
3 2 2 2
ø

344
 345

2. The smallest energy a photon can have corresponds to a transition from the non-
quantized region to E3 . Since the energy difference between E3 and E4 is

DE = E4 - E3 = 9.0 eV - 4.0 eV = 5.0 eV ,

the energy of the photon is Ephoton = K + DE = 2.00 eV + 5.00 eV = 7.00 eV .

346 CHAPTER 39

3. The position of maximum probability density corresponds to the center of the well:
x = L / 2 = (200 pm) / 2 = 100 pm.

(a) The probability of detection at x is given by Eq. 39-11:

2
é 2 æ np ö ù 2 æ np ö
p( x) = y ( x )dx = ê
2
n sin ç x ÷ ú dx = sin 2 ç x ÷ dx
ë L è L øû L è L ø

For n = 3, L = 200 pm, and dx = 2.00 pm (width of the probe), the probability of
detection at x = L / 2 = 100 pm is

2 2 æ 3p L ö 2 æ 3p ö 2 2
p( x = L / 2) = sin ç × ÷ dx = sin 2 ç ÷ dx = dx = ( 2.00 pm ) = 0.020 .
L è L 2ø L è 2 ø L 200 pm

(b) With N = 1000 independent insertions, the number of times we expect the electron to
be detected is n = Np = (1000)(0.020) = 20 .
 347

4. The difference between the energy absorbed and the energy emitted is

hc hc
E photon absorbed - E photon emitted = - .
l absorbed l emitted

Thus, using hc = 1240 eV · nm, the net energy absorbed is

æ 1ö æ 1 1 ö
è lø
(
hcD ç ÷ = 1240eV × nm ç - )
è 400 nm 580 nm ÷ø
= 0.962eV .
348 CHAPTER 39

5. The discussion on the probability of detection for the one-dimensional case can be
readily extended to two dimensions. In analogy to Eq. 39-10, the normalized wave
function in two dimensions can be written as

2 ænp ö 2 æn p ö
y n , n ( x, y ) = y n ( x)y n ( y ) = sin ç x x ÷ × sin ç y y ÷
Lx ç Ly ÷
è Lx ø Ly
x y x y
è ø
4 ænp ö æ n p ö
= sin ç x x ÷ sin ç y y ÷ .
Lx Ly ç ÷
è Lx ø è Ly ø

The probability of detection by a probe of dimension DxDy placed at ( x, y ) is

2 4( DxDy ) 2 æ nxp ö 2 æ nyp ö

p( x, y ) = y nx , n y ( x, y ) DxDy = sin ç x ÷ sin ç y ÷.
Lx Ly ç L ÷
è Lx ø è y ø

With Lx = Ly = L = 150 pm and Dx = Dy = 5.00 pm , the probability of detecting an

electron in (nx , n y ) = (1,3) state by placing a probe at (0.200 L, 0.800 L ) is

4(DxDy ) 2 æ nxp ö æ n p ö 4(5.00 pm)2 æp ö æ 3p ö

p= sin ç x ÷ sin 2 ç y y ÷ = sin 2 ç × 0.200 L ÷ sin 2 ç 0.800 L ÷
Lx Ly è Lx ø ç Ly ÷ (150 pm) 2
èL ø è L ø
è ø
2
æ 5.00 pm ö
= 4ç ÷ sin ( 0.200p ) sin ( 2.40p )
2 2

è 150 pm ø
= 1.4 ´10-3 .
 349

6. (a) We use Eq. 39-44. At r = 0, P(r) µ r2 = 0.

4 2 - 2 a a 4e - 2 4e - 2
(b) At r = a, P ( r ) = a e = = = 10.2 nm -1 .
a3 a 5.29 ´ 10-2 nm

4 16e -4 16e -4
(c) At r = 2a, P ( r ) = 3 ( )
2 -4 a a
2 a e = = -2
= 5.54 nm -1.
a a 5.29 ´ 10 nm
350 CHAPTER 39

7. THINK The Lyman series is associated with transitions to or from the n = 1 level of
the hydrogen atom, while the Balmer series is for transitions to or from the n = 2 level.

EXPRESS The energy E of the photon emitted when a hydrogen atom jumps from a
state with principal quantum number n¢ to a state with principal quantum number n < n¢
is given by
æ 1 1 ö
E = Aç 2 - 2 ÷
èn n¢ ø

where A = 13.6 eV. The frequency f of the electromagnetic wave is given by f = E/h and
the wavelength is given by l = c/f. Thus,

1 f E Aæ 1 1 ö
= = = ç 2- 2÷.
l c hc hc è n n¢ ø

ANALYZE The shortest wavelength occurs at the series limit, for which n¢ = ¥. For the
Balmer series, n = 2 and the shortest wavelength is lB = 4hc/A. For the Lyman series,
n = 1 and the shortest wavelength is lL = hc/A. The ratio is lB/lL = 4.0.

LEARN The energy of the photon emitted associated with the transition of an electron
from n¢ = ¥ ® n = 2 (to become bound) is

13.6 eV
E¥®2 = = 3.4 eV .
22

Similarly, the energy associated with the transition of an electron from n¢ = ¥ ® n = 1 (to
become bound) is
13.6 eV
E1®¥ = = 13.6 eV .
12
 351

8. From Fig. 39-9, we see that the sum of the kinetic and potential energies in that
particular finite well is 233 eV. The potential energy is zero in the region 0 < x < L. If the
kinetic energy of the electron is detected while it is in that region (which is the only
region where this is likely to happen), we should find K = 233 eV.
352 CHAPTER 39

9. THINK The energy of the hydrogen atom is quantized.

EXPRESS If kinetic energy is not conserved, some of the neutron’s initial kinetic energy
could be used to excite the hydrogen atom. The least energy that the hydrogen atom can
accept is the difference between the first excited state (n = 2) and the ground state (n = 1).
Since the energy of a state with principal quantum number n is –(13.6 eV)/n2, the
smallest excitation energy is
-13.6 eV -13.6eV
DE = E2 - E1 = - = 10.2 eV .
( 2) (1)
2 2

ANALYZE The neutron, with a kinetic energy of 6.0 eV, does not have sufficient kinetic
energy to excite the hydrogen atom, so the hydrogen atom is left in its ground state and
all the initial kinetic energy of the neutron ends up as the final kinetic energies of the
neutron and atom. The collision must be elastic.

LEARN The minimum kinetic energy the neutron must have in order to excite the
hydrogen atom is 10.2 eV.
 353

10. We are looking for the values of the ratio

Enx ,ny Fn 2 I = FG n
n 2y IJ
h 8mL
2 2
= L2 GH L
x
2
x
+
L JK H
2
y
2
x
1
+ n 2y
4 K
and the corresponding differences.

(a) For nx = ny = 1, the ratio becomes 1 + 41 = 125

. .

bg
(b) For nx = 1 and ny = 2, the ratio becomes 1 + 41 4 = 2.00. One can check (by computing
other (nx, ny) values) that this is the next to lowest energy in the system.

(c) The lowest set of states that are degenerate are (nx, ny) = (1, 4) and (2, 2). Both of
b g
these states have that ratio equal to 1 + 41 16 = 5.00.

bg
(d) For nx = 1 and ny = 3, the ratio becomes 1 + 14 9 = 3.25. One can check (by computing
other (nx, ny) values) that this is the lowest energy greater than that computed in part (b).
The next higher energy comes from (nx, ny) = (2, 1) for which the ratio is 4 + 41 1 = 4.25. bg
The difference between these two values is 4.25 – 3.25 = 1.00.
354 CHAPTER 39

11. Schrödinger’s equation for the region x > L is

d 2y 8p 2m
+ 2 E - U 0 y = 0.
dx 2 h

If y = De2kx, then d 2y/dx2 = 4k2De2kx = 4k2y and

d 2y 8p 2 m 8p 2m
+ E - U 0 y = 4 k 2
y + E - U0 y .
dx 2 h2 h2

This is zero provided

p
k=
h
b
2m U 0 - E .g
The proposed function satisfies Schrödinger’s equation provided k has this value. Since
U0 is greater than E in the region x > L, the quantity under the radical is positive. This
means k is real. If k is positive, however, the proposed function is physically unrealistic.
It increases exponentially with x and becomes large without bound. The integral of the
probability density over the entire x-axis must be unity. This is impossible if y is the
proposed function.
 355

( )( )
12. From Eq. 39-6, DE = hf = 4.14 ´ 10-15 eV × s 5.6 ´ 1014 Hz = 2.3eV .
356 CHAPTER 39

13. Since Dr is small, we may calculate the probability using p = P(r) Dr, where P(r) is
the radial probability density. The radial probability density for the ground state of
hydrogen is given by Eq. 39-44:

P (r ) =
FG IJ
4r 2 -2 r / a
e
H K
a3
where a is the Bohr radius.

(a) Here, r = 0.500a and Dr = 0.010a. Then,

æ 4 r 2 Dr ö
P = ç 3 ÷ e -2 r / a = 4(0.500)2 (0.010)e -1 = 3.68 ´10 -3 » 3.7 ´10-3.
è a ø

(b) We set r = 1.00a and Dr = 0.010a. Then,

æ 4r 2 Dr ö
P = ç 3 ÷ e -2 r / a = 4(1.00)2 (0.010)e -2 = 5.41´10-3 » 5.4 ´10-3.
è a ø
 357

14. From Eq. 39-11, the condition of zero probability density is given by

æ np ö np
sin ç x÷ = 0 Þ x = mp
è L ø L

where m is an integer. The fact that x = 0.300 L and x = 0.400 L have zero probability
density implies
sin ( 0.300np ) = sin ( 0.400np ) = 0

which can be satisfied for n = 10m , where m = 1, 2,... However, since the probability
density is nonzero between x = 0.300 L and x = 0.400 L , we conclude that the electron is
in the n = 10 state. The change of energy after making a transition to n¢ = 9 is then equal
to
( )
2
6.63 ´ 10-34 J × s
| DE | =
h2
(
n - n¢ =
2 2
) (10 2
)
- 9 2 = 3.54 ´ 10-17 J .
8mL2
( )( )
2
8 9.11´ 10 -31 kg 1.80 ´ 10-10 m
358 CHAPTER 39

15. (a) and (b) Letting a = 5.292 ´ 10– 11 m be the Bohr radius, the potential energy
becomes

U =-
e2
=
c hc
8.99 ´ 109 N × m2 C 2 1602
. h
´ 10-19 C
2

= - 4.36 ´ 10-18 J = -27.2 eV .

4 pe 0 a 5.292 ´ 10-11 m

The kinetic energy is K = E – U = (– 13.6 eV) – (– 27.2 eV) = 13.6 eV.

 359

16. Conservation of linear momentum of the atom-photon system requires that

hf
precoil = pphoton Þ m p vrecoil =
c

where we use Eq. 39-7 for the photon and use the classical momentum formula for the
atom (since we expect its speed to be much less than c). Thus, from Eq. 39-6 and Table
37-3,

vrecoil =
DE
=
E4 - E1
=
( )(
-13.6eV 3-2 - 1-2 )
= 3.9 m s .
( ) (
mp c mp c 2 c )(
938 ´ 106 eV 2.998 ´ 108 m s )
360 CHAPTER 39

17. (a) We take the electrostatic potential energy to be zero when the electron and proton
are far removed from each other. Then, the final energy of the atom is zero and the work
done in pulling it apart is W = – Ei, where Ei is the energy of the initial state. The energy
of the initial state is given by Ei = (–13.6 eV)/n2, where n is the principal quantum
number of the state. For the ground state, n = 1 and W = 13.6 eV.

(b) For the state with n = 2, W = (13.6 eV)/(2)2 = 3.40 eV.

 361

18. From Eq. 39-11, the condition of zero probability density is given by

æ np ö np
sin ç x÷ = 0 Þ x = mp
è L ø L

where m is an integer. The fact that x = 0.300 L and x = 0.400 L have zero probability
density implies
sin ( 0.300np ) = sin ( 0.400np ) = 0

which can be satisfied for n = 10m , where m = 1, 2,... However, since the probability
density is nonzero between x = 0.300 L and x = 0.400 L , we conclude that the electron is
in the n = 10 state. The change of energy after making a transition to n¢ = 9 is then equal
to
( )
2
6.63 ´ 10-34 J × s
| DE | =
h2
(
n - n¢ =
2 2
) (10 2
)
- 9 2 = 3.54 ´ 10-17 J .
8mL2 ( )( )
2
8 9.11´ 10 -31 kg 1.80 ´ 10-10 m
362 CHAPTER 39

19. THINK The probability density is given by |y nlml (r ,q ) |2 , where y nlml (r ,q ) is the
wave function.

EXPRESS To calculate | y nlml |2 = y *nlml y nlml , we multiply the wave function by its
complex conjugate. If the function is real, then y *nlml = y nlml . Note that e + if and e - if are
complex conjugates of each other, and eif e– if = e0 = 1.

ANALYZE (a) y210 is real. Squaring it gives the probability density:

r2
| y 210 |2 = e - r / a cos 2 q .
32pa 5

(b) Similarly,
r2
|y 21+1 | =
2
e - r / a sin 2 q
64 pa 5

and
r2
| y 21-1 |2 = e - r / a sin 2 q .
64pa 5

The last two functions lead to the same probability density.

(c) For ml = 0, the probability density |y 210 |2 decreases with radial distance from the
nucleus. With the cos 2 q factor, |y 210 |2 is greatest along the z axis where q = 0. This is
consistent with the dot plot of Fig. 39-23(a).

Similarly, for ml = ±1, the probability density | y 21±1 |2 decreases with radial distance
from the nucleus. With the sin 2 q factor, | y 21±1 |2 is greatest in the xy-plane where q =
90°. This is consistent with the dot plot of Fig. 39-23(b).

(d) The total probability density for the three states is the sum:

r2 -r / a é 1 2 1 2 ù r2
| y 210 |2 + | y 21+1 |2 + | y 21-1 |2 = e ê cos 2
q + sin q + sin q = -r / a
ú 32p a5 e .
32p a 5 ë 2 2 û

The trigonometric identity cos2 q + sin2 q = 1 is used. We note that the total probability
density does not depend on q or f; it is spherically symmetric.

LEARN The wave functions discussed above are for the hydrogen states with n = 2 and
l = 1. Since the angular momentum is nonzero, the probability densities are not
spherically symmetric, but depend on both r and q.
363
364 CHAPTER 39

20. We are looking for the values of the ratio

E n x ,n y ,nz Fn 2
n y2 nz2I d i
h 8mL
2 2
= L2 GH L
x
2
x
+
L 2
y
+
L2zJK
= nx2 + n y2 + nz2

and the corresponding differences.

(a) For nx = ny = nz = 1, the ratio becomes 1 + 1 + 1 = 3.00.

(b) For nx = ny = 2 and nz = 1, the ratio becomes 4 + 4 + 1 = 9.00. One can check (by
computing other (nx, ny, nz) values) that this is the third lowest energy in the system. One
can also check that this same ratio is obtained for (nx, ny, nz) = (2, 1, 2) and (1, 2, 2).

(c) For nx = ny = 1 and nz = 3, the ratio becomes 1 + 1 + 9 = 11.00. One can check (by
computing other (nx, ny, nz) values) that this is three “steps” up from the lowest energy in
the system. One can also check that this same ratio is obtained for (nx, ny, nz) = (1, 3, 1)
and (3, 1, 1). If we take the difference between this and the result of part (b), we obtain
11.0 – 9.00 = 2.00.

(d) For nx = ny = 1 and nz = 2, the ratio becomes 1 + 1 + 4 = 6.00. One can check (by
computing other (nx, ny, nz) values) that this is the next to the lowest energy in the system.
One can also check that this same ratio is obtained for (nx, ny, nz) = (2, 1, 1) and (1, 2, 1).
Thus, three states (three arrangements of (nx, ny, nz) values) have this energy.

(e) For nx = 1, ny = 2 and nz = 3, the ratio becomes 1 + 4 + 9 = 14.0. One can check (by
computing other (nx, ny, nz) values) that this is five “steps” up from the lowest energy in
the system. One can also check that this same ratio is obtained for (nx, ny, nz) = (1, 3, 2),
(2, 3, 1), (2, 1, 3), (3, 1, 2) and (3, 2, 1). Thus, six states (six arrangements of (nx, ny, nz)
values) have this energy.
 365

21. Since En µ L– 2 in Eq. 39-4, we see that if L is doubled, then E1 becomes (2.6 eV)(2)– 2
= 0.65 eV.
366 CHAPTER 39

22. In analogy to Eq. 39-10, the normalized wave function in two dimensions can be
written as
2 ænp ö 2 æn p ö
y nx , ny ( x, y ) = y nx ( x)y ny ( y ) = sin ç x x ÷ × sin ç y y ÷
Lx ç Ly ÷
è Lx ø Ly è ø
4 ænp ö æn p ö
= sin ç x x ÷ sin ç y y ÷ .
Lx Ly ç ÷
è Lx ø è Ly ø

The probability of detection by a probe of dimension DxDy placed at ( x, y ) is

2 4( DxDy ) 2 æ nxp ö 2 æ nyp ö

p( x, y ) = y nx , n y ( x, y ) DxDy = sin ç x ÷ sin ç y ÷.
Lx Ly ç L ÷
è Lx ø è y ø

A detection probability of 0.0420 of a ground-state electron ( nx = n y = 1 ) by a probe of

area DxDy = 400 pm2 placed at ( x, y ) = ( L / 8, L / 8) implies

2
4(400 pm 2 ) 2 æ p L ö 2 æ p L ö æ 20 pm ö 4æpö
0.0420 = sin ×
çè L 8 ÷ø sin ×
çè L 8 ÷ø = 4 çè L ÷ø sin çè 8 ÷ø .
L2

Solving for L, we get L = 28.6 pm .

 367

23. THINK The ground state of the hydrogen atom corresponds to n = 1, l = 0, and
ml = 0.

EXPRESS The proposed wave function is

1
y= e -r a
pa 32

where a is the Bohr radius. Substituting this into the right side of Schrödinger’s equation,
our goal is to show that the result is zero.

ANALYZE The derivative is

dy 1
=- e -r a
dr pa 52

so
dy r2
r2
=- e -r a
dr pa 52

and
FG
1 d 2 dy IJ 1 LM OP
2 1 -r a 1 2 1
y.
LM OP
r 2 dr H
r
dr
=
K pa5 2
-
N + e
r a
= - +
Q
a r a N Q
The energy of the ground state is given by E = -me4 8e 20 h2 and the Bohr radius is given
by a = h 2 e 0 pme 2 , so E = -e 2 8pe 0a. The potential energy is given by

U = -e 2 4pe 0r ,
so
8p 2 m
E - U y =
8p 2 m
-
e2 LM
+
e2
y =
OP
8p 2 m e 2 1 2
- + y
LM OP
h 2
h 2
N
8pe 0 a 4 pe 0 r h 8pe 0
2
Q a r N Q
=
pme 2 LM- 1 + 2 OP y = 1 LM- 1 + 2 OP y .
h2 e 0 N a rQ a N a rQ
The two terms in Schrödinger’s equation cancel, and the proposed function y satisfies
that equation.

LEARN The radial probability density of the ground state of hydrogen atom is given by
Eq. 39-44:
1 4
P(r ) = | y |2 (4p r 2 ) = 3 e -2r a (4p r 2 ) = 3 r 2e -2r a .
pa a

A plot of P(r) is shown in Fig. 39-20.

368 CHAPTER 39

24. We follow Sample Problem — “Detection potential in a 1D infinite potential well” in

the presentation of this solution. The integration result quoted below is discussed in a
little more detail in that Sample Problem. We note that the arguments of the sine
functions used below are in radians.

(a) The probability of detecting the particle in the region 0 £ x £ L / 4 is

p /4
æ 2 öæ L ö p /4 2 2 æ y sin 2 y ö
ç L ÷ ç p ÷ ò0 sin y dy = p ç 2 - 4 ÷ = 0.091.
è øè ø è ø 0

(b) As expected from symmetry,

p
æ 2 öæ L ö p 2 æ y sin 2 y ö
ç L ÷ç p ÷ òp / 4 sin y dy = p ç 2 - 4 ÷ = 0.091.
2

è øè ø è ø p /4

(c) For the region L / 4 £ x £ 3L / 4 , we obtain

3p / 4
æ 2 ö æ L ö 3p / 4 2 2 æ y sin 2 y ö
ç L ÷ ç p ÷ òp / 4 sin y dy = p ç 2 - 4 ÷ = 0.82
è øè ø è ø p /4

which we could also have gotten by subtracting the results of part (a) and (b) from 1; that
is, 1 – 2(0.091) = 0.82.
 369

25. (a) We use Eq. 39-39. At r = a,

2
æ 1 ö 1 1
y (r) = ç
2
e - a a ÷ = 3 e -2 = e -2 = 291nm -3 .
è pa ø pa p ( 5.29 ´10 nm )
32 - 2 3

(b) We use Eq. 39-44. At r = a,

4 2 - 2 a a 4e - 2 4e - 2
P (r) = a e = = = 10.2 nm -1 .
a3 a 5.29 ´ 10-2 nm
370 CHAPTER 39

26. Using Eq. 39-6 and hc = 1240 eV · nm, we find

hc 1240 eV × nm
DE = Ephoton = = = 12.09 eV.
l 106.6 nm

Therefore, nlow = 1, but what precisely is nhigh?

13.6 eV 13.6 eV
Ehigh = Elow + DE Þ - =- + 12.09 eV
n 2
12

which yields n = 3. Thus, the transition is from the n = 3 to the n = 1 state.

(a) The higher quantum number is n = 3.

(b) The lower quantum number is n = 1.

(c) Referring to Fig. 39-18, we see that this must be one of the Lyman series transitions.
 371

27. (a) Since energy is conserved, the energy E of the photon is given by E = Ei – Ef,
where Ei is the initial energy of the hydrogen atom and Ef is the final energy. The electron
energy is given by (– 13.6 eV)/n2, where n is the principal quantum number. Thus,

-13.6 eV -13.6eV
E = E3 - E1 = - = 12.1eV .
( 3) (1)
2 2

(b) The photon momentum is given by

p= =
b gc
. ´ 10-19 J eV
E 12.1eV 160 h
= 6.45 ´ 10-27 kg × m s .
c 3.00 ´ 10 m s
8

hc 1240 eV × nm
(c) Using hc = 1240 eV · nm, the wavelength is l = = = 102 nm.
E 12.1eV
372 CHAPTER 39

28. (a) The calculation is shown in Sample Problem — “Light emission from a hydrogen
atom.” The difference in the values obtained in parts (a) and (b) of that Sample Problem
is 122 nm – 91.4 nm » 31 nm.

(b) We use Eq. 39-1. For the Lyman series,

2.998 ´ 108 m s 2.998 ´ 108 m s

Df = -9
- -9
= 8.2 ´ 1014 Hz .
91.4 ´ 10 m 122 ´ 10 m

(c) Figure 39-18 shows that the width of the Balmer series is 656.3 nm – 364.6 nm »
292 nm » 0.29 m m .

(d) The series limit can be obtained from the ¥ ® 2 transition:

2.998 ´ 108 m s 2.998 ´ 108 m s

Df = -9
- -9
= 3.65 ´ 1014 Hz » 3.7 ´ 1014 Hz.
364.6 ´ 10 m 656.3 ´10 m
 373

29. We can use the mc2 value for an electron from Table 37-3 (511 ´ 103 eV) and hc =
1240 eV · nm by rewriting Eq. 39-4 as

En =
n2h2
=
n 2 hc
2
b g
8mL2 8 mc 2 L2
.
c h
(a) The first excited state is characterized by n = 2, and the third by n' = 4. Thus,

( hc ) (1240eV × nm )
2 2

DE =
8 ( mc ) L
( n¢ 2
-n 2
)= (4 2
- 22 ) = ( 6.02eV ) (16 - 4 )
8 ( 511´ 103 eV ) ( 0.250nm )
2 2 2

= 72.2eV .

Now that the electron is in the n' = 4 level, it can “drop” to a lower level (n'') in a variety
of ways. Each of these drops is presumed to cause a photon to be emitted of wavelength

hc 8 ( mc 2 ) L2
l= = .
En¢ - En¢¢ hc ( n¢2 - n¢¢2 )

For example, for the transition n' = 4 to n'' = 3, the photon emitted would have
wavelength
8 ( 511´103 eV ) ( 0.250 nm )
2

l= = 29.4 nm,
(1240 eV × nm ) ( 42 - 32 )

and once it is then in level n'' = 3 it might fall to level n''' = 2 emitting another photon.
Calculating in this way all the possible photons emitted during the de-excitation of this
system, we obtain the following results:

(b) The shortest wavelength that can be emitted is l 4®1 = 13.7nm.

(c) The second shortest wavelength that can be emitted is l 4®2 = 17.2nm.

(d) The longest wavelength that can be emitted is l 2®1 = 68.7 nm.

(e) The second longest wavelength that can be emitted is l 3®2 = 41.2 nm.

(f) The possible transitions are shown next. The energy levels are not drawn to scale.
374 CHAPTER 39

(g) A wavelength of 29.4 nm corresponds to 4 ® 3 transition. Thus, it could make either

the 3 ® 1 transition or the pair of transitions: 3 ® 2 and 2 ® 1 . The longest wavelength
that can be emitted is l 2®1 = 68.7 nm.

(h) The shortest wavelength that can next be emitted is l 3®1 = 25.8nm.
 375

30. From Sample Problem — “ Probability of detection of the electron in a hydrogen

atom,” we know that the probability of finding the electron in the ground state of the
hydrogen atom inside a sphere of radius r is given by

c
p ( r ) = 1 - e -2 x 1 + 2 x + 2 x 2 h
where x = r/a. Thus the probability of finding the electron between the two shells
indicated in this problem is given by

p(a < r < 2a) = p(2a ) - p (a) = éë1 - e -2 x (1 + 2 x + 2 x 2 ) ùû - éë1 - e -2 x (1 + 2 x + 2 x 2 ) ùû

x=2 x =1

= 0.439.
376 CHAPTER 39

31. Let the quantum numbers of the pair in question be n and n + 1, respectively. We note
that

E n +1 - E n =
b g
n + 1 h2 n2h 2
2

- =
b g
2n + 1 h 2
8mL2 8mL2 8mL2

Therefore, En+1 – En = (2n + 1)E1. Now

b g
En+1 - En = E5 = 52 E1 = 25E1 = 2n + 1 E1 ,

which leads to 2n + 1 = 25, or n = 12. Thus,

(a) The higher quantum number is n + 1 = 12 + 1 = 13.

(b) The lower quantum number is n = 12.

(c) Now let

b g
En+1 - En = E6 = 62 E1 = 36 E1 = 2n + 1 E1 ,

which gives 2n + 1 = 36, or n = 17.5. This is not an integer, so it is impossible to find the
pair that fits the requirement.
 377

32. (a) The plot shown below for |y200(r)|2 is to be compared with the dot plot of Fig.
39-21. We note that the horizontal axis of our graph is labeled “r,” but it is actually r/a
(that is, it is in units of the parameter a). Now, in the plot below there is a high central
peak between r = 0 and r ~ 2a, corresponding to the densely dotted region around the
center of the dot plot of Fig. 39-21. Outside this peak is a region of near-zero values
centered at r = 2a, where y200 = 0. This is represented in the dot plot by the empty ring
surrounding the central peak. Further outside is a broader, flatter, low peak that reaches
its maximum value at r = 4a. This corresponds to the outer ring with near-uniform dot
density, which is lower than that of the central peak.

(b) The extrema of y2(r) for 0 < r < ¥ may be found by squaring the given function,
differentiating with respect to r, and setting the result equal to zero:

1 ( r - 2a ) ( r - 4a ) - r / a
- e =0
32 a 6p

which has roots at r = 2a and r = 4a. We can verify directly from the plot above that r =
4a is indeed a local maximum of y 2200 (r ). As discussed in part (a), the other root (r = 2a)
is a local minimum.

(c) Using Eq. 39-43 and Eq. 39-41, the radial probability is

P200 (r ) = 4 pr y
r2 r FG IJ e
2
-r /a
(r ) = 3 2 -
H K
2 2
200 .
8a a
(d) Let x = r/a. Then

2
¥ ¥ r2 æ r ö -r / a 1 ¥ 2 ¥
ò P200 (r ) dr = ò ò ò
2 -x
ç 2 - ÷ e dr = x (2 - x ) e dx = ( x 4 - 4 x3 + 4 x 2 )e - x dx
0 0 8a è
3
aø 8 0 0

1
= [4! - 4(3!) + 4(2!)] = 1
8

where we have used the integral formula z ¥

0
x n e - x dx = n ! .
378 CHAPTER 39

33. THINK The radial probability function for the ground state of hydrogen is

P(r) = (4r2/a3)e– 2r/a,

where a is the Bohr radius.

EXPRESS We want to evaluate the integral

of Appendix E is an integral of this form:
z0
¥
P(r ) dr. Equation 15 in the integral table

¥ n!
ò0
x n e - ax dx =
a n +1
.

ANALYZE We set n = 2 and replace a in the given formula with 2/a and x with r. Then

z0
¥
P (r )dr =
4
a3 z
0
¥
r 2 e -2 r / a dr =
4 2
a (2 a ) 3
3
= 1.

LEARN The integral over the radial probability function P(r) must be equal to 1. This
means that in a hydrogen atom, the electron must be somewhere in the space surrounding
the nucleus.
 379

34. (a) We use Eq. 39-44. At r = 0, P(r) µ r2 = 0.

4 2 - 2 a a 4e - 2 4e - 2
(b) At r = a, P ( r ) = a e = = = 10.2 nm -1 .
a3 a 5.29 ´ 10-2 nm

4 16e -4 16e -4
(c) At r = 2a, P ( r ) = 3 ( )
2 -4 a a
2 a e = = -2
= 5.54 nm -1.
a a 5.29 ´ 10 nm
380 CHAPTER 39

35. According to Sample Problem — “ Probability of detection of the electron in a

hydrogen atom,” the probability the electron in the ground state of a hydrogen atom can
be found inside a sphere of radius r is given by

c
p ( r ) = 1 - e -2 x 1 + 2 x + 2 x 2 h
where x = r/a and a is the Bohr radius. We want r = a, so x = 1 and

p(a) = 1 - e -2 (1 + 2 + 2) = 1 - 5e -2 = 0.323.

The probability that the electron can be found outside this sphere is 1 – 0.323 = 0.677. It
can be found outside about 68% of the time.
 381

36. With m = mp = 1.67 ´ 10– 27 kg, we obtain

æ
( ) ö
2
æ h2 ö 2 6.63 ´ 10-34 J.s
E1 = ç 2÷
n =ç ()
÷ 1 2 = 2.28 ´ 10-21 J = 0.0143eV.
è 8mL ø (
ç 8(1.67 ´ 10 -27 kg) 120 ´ 1012 m
) ÷
2
è ø

Alternatively, we can use the mc2 value for a proton from Table 37-3 (938 ´ 106 eV) and
hc = 1240 eV · nm by writing Eq. 39-4 as

( )
2
n2 h2 n hc
2

En = =
( )
.
8mL2 8 mp c 2 L2

This alternative approach is perhaps easier to plug into, but it is recommended that both
approaches be tried to find which is most convenient.
382 CHAPTER 39

37. The radial probability function for the ground state of hydrogen is

P(r) = (4r2/a3)e– 2r/a,

where a is the Bohr radius. (See Eq. 39-44.) The integral table of Appendix E may be
used to evaluate the integral ravg = z0
formula with 2/a (and x with r), we obtain
¥
rP(r ) dr. Setting n = 3 and replacing a in the given

¥ 4 ¥ 4 6
ravg = ò rP(r ) dr = ò r 3e-2r / a dr = = 1.5a .
0 a3 0 a 3 ( 2 a )4

Let the quantum numbers of the pair in question be n and n + 1, respectively. Then

En+1 – En = E1 (n + 1)2 – E1n2 = (2n + 1)E1.

Letting

b g b g c
E n +1 - E n = 2n + 1 E1 = 3 E 4 - E 3 = 3 4 2 E1 - 32 E1 = 21E1 , h
we get 2n + 1 = 21, or n = 10. Thus,

(a) the higher quantum number is n + 1 = 10 + 1 = 11, and

(b) the lower quantum number is n = 10.

(c) Now letting

b g b g c
E n +1 - E n = 2n + 1 E1 = 2 E 4 - E 3 = 2 4 2 E1 - 32 E1 = 14 E1 , h
we get 2n + 1 = 14, which does not have an integer-valued solution. So it is impossible to
find the pair of energy levels that fits the requirement.
 383

38. Let the quantum numbers of the pair in question be n and n + 1, respectively. Then

En+1 – En = E1 (n + 1)2 – E1n2 = (2n + 1)E1.

Letting

b g b g c h
E n +1 - E n = 2n + 1 E1 = 3 E 4 - E 3 = 3 4 2 E1 - 32 E1 = 21E1 ,

we get 2n + 1 = 21, or n = 10. Thus,

(a) the higher quantum number is n + 1 = 10 + 1 = 11, and

(b) the lower quantum number is n = 10.

(c) Now letting

b g b g c h
E n +1 - E n = 2n + 1 E1 = 2 E 4 - E 3 = 2 4 2 E1 - 32 E1 = 14 E1 ,

we get 2n + 1 = 14, which does not have an integer-valued solution. So it is impossible to

find the pair of energy levels that fits the requirement.
384 CHAPTER 39

39. As illustrated in Fig. 39-24, the quantum number n in question satisfies r = n2a.
Letting r = 1.0 mm, we solve for n:
r . ´ 10-3 m
10
n= = » 4.3 ´ 103 .
a 5.29 ´ 10-11 m
 385

40. a) DE = – (13.6 eV)(4– 2 – 1– 2) = 12.8 eV.

(b) There are 6 possible energies associated with the transitions 4 ® 3, 4 ® 2, 4 ® 1,

3 ® 2, 3 ® 1 and 2 ® 1.

(c) The greatest energy is E4®1 = 12.8 eV.

(d) The second greatest energy is E3®1 = - (13.6eV ) ( 3-2 - 1-2 ) = 12.1 eV .

(e) The third greatest energy is E2®1 = - (13.6eV ) ( 2-2 - 1-2 ) = 10.2 eV .

(f) The smallest energy is E4®3 = - (13.6eV ) ( 4-2 - 3-2 ) = 0.661 eV .

(g) The second smallest energy is E3® 2 = - (13.6eV ) ( 3-2 - 2-2 ) = 1.89 eV .

(h) The third smallest energy is E4® 2 = - (13.6eV ) ( 4 -2 - 2 -2 ) = 2.55 eV.

386 CHAPTER 39

41. According to Fig. 39-9, the electron’s initial energy is 106 eV. After the additional
energy is absorbed, the total energy of the electron is 106 eV + 400 eV = 506 eV. Since it
is in the region x > L, its potential energy is 450 eV, so its kinetic energy must be 506 eV
– 450 eV = 56 eV.
 387

42. We can use the mc2 value for an electron from Table 37-3 (511 ´ 103 eV) and hc =
1240 eV · nm by writing Eq. 39-20 as

F
2h 2 nx2 n y
2
I b g Fn
hc
2 2 I.
n 2y
E nx ,ny = GH
8m Lx Ly
2 JK c h GH L
+ 2 =
8 mc 2
x
2
x
+
L JK
2
y

For nx = ny = 1, we obtain

(1240eV × nm ) æ ö
2
1 1
E1,1 = ç + ÷ = 0.734 eV.
8 ( 511´103 eV ) çè ( 0.800nm ) (1.600nm ) ÷ø
2 2
388 CHAPTER 39

43. THINK The probability that the electron is found in any interval is given by
z
P = y dx , where the integral is over the interval.
2

EXPRESS If the interval width Dx is small, the probability can be approximated by P =

|y|2 Dx, where the wave function is evaluated for the center of the interval, say. For an
electron trapped in an infinite well of width L, the ground state probability density is
2FG IJ
y = sin 2
px
H K
2
,
L L
so
FG IJ FG IJ
2 Dx px
P=
H K H K
L
sin 2
L
.

ANALYZE (a) We take L = 100 pm, x = 25 pm, and Dx = 5.0 pm. Then,

P=
LM 2b5.0 pmg OP sin LM pb25 pmg OP = 0.050.
2

N 100 pm Q N 100 pm Q
(b) We take L = 100 pm, x = 50 pm, and Dx = 5.0 pm. Then,

P=
LM 2b5.0 pmg OP sin LM pb50 pmg OP = 010
2
. .
N 100 pm Q N 100 pm Q
(c) We take L = 100 pm, x = 90 pm, and Dx = 5.0 pm. Then,

P=
LM 2b5.0 pmg OP sin LM pb90 pmg OP = 0.0095.
2

N 100 pm Q N 100 pm Q
LEARN The probability as a function of x is plotted next. As expected, the probability of
detecting the electron is highest near the center of the well at x = L/2 = 50 pm.
 389

44. The frequency of the light that will excite the electron from the state with quantum
number ni to the state with quantum number nf is

DE h
2 ( f
f = = n 2 - ni2 )
h 8mL

and the wavelength of the light is

c 8mL2 c
l= =
d
f h n2f - ni2
.
i
The width of the well is
l hc (n2f - ni2 )
L= .
8mc 2

The longest wavelength shown in Figure 39-27 is l = 80.78 nm, which corresponds to a
jump from ni = 2 to n f = 3 . Thus, the width of the well is

l hc(n 2f - ni2 ) (80.78 nm)(1240eV × nm)(32 - 2 2 )

L= = = 0.350nm = 350 pm.
8mc 2 8(511 ´ 103 eV)
390 CHAPTER 39

45. According to Eq. 39-4, En µ L– 2. As a consequence, the new energy level E'n satisfies

En¢ FG IJ = FG L IJ
L¢
-2 2
1
En
=
H K H L¢ K
L
= ,
2

which gives L ¢ = 2 L. Thus, the ratio is L¢ / L = 2 = 1.41.

 391

46. The statement that there are three probability density maxima along x = Lx / 2 implies
that n y = 3 (see for example, Figure 39-6). Since the maxima are separated by 2.00 nm,
the width of L y is Ly = n y (2.00 nm) = 6.00 nm. Similarly, from the information given
along y = Ly / 2 , we find nx = 5 and Lx = nx (3.00 nm) = 15.0 nm. Thus, using Eq. 39-20,
the energy of the electron is

h 2 æ nx2 n y ö (6.63 ´ 10-34 J × s)2 é ù

2
1 1
Enx , ny = çç 2 + 2 ÷
= +
8m è Lx Ly ÷ø 8(9.11´ 10 kg) ë (3.00 ´ 10 m) (2.00 ´ 10 m) úû
- 31 ê - 9 2 -9 2

= 2.2 ´ 10-20 J .
392 CHAPTER 39

47. To estimate the energy, we use Eq. 39-4, with n = 1, L equal to the atomic diameter,
and m equal to the mass of an electron:

(1) ( 6.63 ´10-34 J × s )

2 2
h2
E=n 2
= = 3.07 ´ 10-10 J=1920MeV » 1.9 GeV.
8mL2 8 ( 9.11´ 10-31 kg )(1.4 ´10 -14 m )2
 393

48. We first note that since h = 6.626 ´ 10–34 J·s and c = 2.998 ´ 108 m/s,

hc =
(6.626 ´ 10 J × s)(2.998 ´ 10 m/s)= 1240eV × nm.
-34 8

(1.602 ´ 10 J/eV )(10 m/nm )

-19 -9

Using the mc2 value for an electron from Table 37-3 (511 ´ 103 eV), Eq. 39-4 can be
rewritten as

En =
n2 h2
=
n 2 hc
2
b g
8mL2 8 mc 2 L2
.
c h
The energy to be absorbed is therefore

DE = E4 -E =
(5 2
)
- 12 h 2
=
( )
24 hc
2

=
(
24 1240eV × nm )
2

= 144eV.
1
8me L2 ( )
8 me c 2 L2 (
8 511 ´ 103 eV )(0.250nm )
2
394 CHAPTER 39

49. For an electron inside a cubical box of widths Lx = Ly = Lz = L, the quantized

energies are given by, in multiple of h2 8mL2 ,

Enx ,ny , nz
= ( nx2 + n 2y + nz2 )
h2 8mL2

The frequencies emitted are given by f = DE/h. For a transition from the second excited
state (2, 2, 1) to the ground state (1, 1, 1), we find

b
f = 9.00 - 3.00 gFGH 8mLh IJK = b6.00gFGH 8mLh IJK .
2 2

In the following, we omit the h/8mL2 factors. For a transition between the fourth excited
state and the ground state, we have f = 12.00 – 3.00 = 9.00. For a transition between the
third excited state and the ground state, we have f = 11.00 – 3.00 = 8.00. For a transition
between the third excited state and the first excited state, we have f = 11.00 – 6.00 = 5.00.
For a transition between the fourth excited state and the third excited state, we have f =
12.00 – 11.00 = 1.00. For a transition between the third excited state and the second
excited state, we have f = 11.00 – 9.00 = 2.00. For a transition between the second
excited state and the first excited state, we have f = 9.00 – 6.00 = 3.00, which also results
from some other transitions.

(a) From the above, we see that there are 7 frequencies.

(b) The lowest frequency is, in units of h/8mL2, 1.00.

(c) The second lowest frequency is, in units of h/8mL2, 2.00.

(d) The third lowest frequency is, in units of h/8mL2, 3.00.

(e) The highest frequency is, in units of h/8mL2, 9.00.

(f) The second highest frequency is, in units of h/8mL2, 8.00.

(g) The third highest frequency is, in units of h/8mL2, 6.00.

 395

50. a) The energy level corresponding to the probability density distribution shown in Fig.
39-21 is the n = 2 level. Its energy is given by

13.6eV
E2 = - = -3.4 eV.
22

(b) As the electron is removed from the hydrogen atom the final energy of the proton-
electron system is zero. Therefore, one needs to supply at least 3.4 eV of energy to the
system in order to bring its energy up from E2 = – 3.4 eV to zero. (If more energy is
supplied, then the electron will retain some kinetic energy after it is removed from the
atom.)
396 CHAPTER 39

51. Using E = hc / l = (1240 eV × nm)/l , the energies associated with la , lb and lc are

hc 1240 eV × nm
Ea = = = 85.00 eV
la 14.588 nm
hc 1240 eV × nm
Eb = = = 256.0 eV
lb 4.8437 nm
hc 1240 eV × nm
Ec = = = 426.0 eV.
lc 2.9108 nm
The ground-state energy is

E1 = E4 - Ec = 450.0 eV - 426.0 eV = 24.0 eV .

Since Ea = E2 - E1 , the energy of the first excited state is

E2 = E1 + Ea = 24.0 eV + 85.0 eV = 109 eV .

 397

52. (a) The ground-state energy is

æ h 2 ö 2 æç ( 6.63 ´ 10-34 J × s ) ö
2

E1 = ç n = ÷ (1) 2 = 1.51´ 10-18 J

2 ÷
è 8m L ø ç 8(9.11´ 10 -31 kg) ( 200 ´ 10-12 m )2 ÷
e
è ø
= 9.42eV.

(b) With mp = 1.67 ´ 10– 27 kg, we obtain

æ h2 ö 2 æ ( 6.63 ´ 10-34 J × s ) ö
2

E1 = ç n = ç ÷ (1) 2 = 8.225 ´ 10-22 J

ç 8m p L2 ÷÷ ç 8(1.67 ´ 10 -27 kg) ( 200 ´10 -12 m ) ÷
2
è ø è ø
-3
= 5.13 ´ 10 eV.
398 CHAPTER 39

53. We can use the mc2 value for an electron from Table 37-3 (511 ´ 103 eV) and hc =
1240 eV · nm by writing Eq. 39-4 as

En =
n2h2
=
n 2 hc b g 2

8mL2 8 mc 2 L2c h
.

For n = 3, we set this expression equal to 4.7 eV and solve for L:

L=
b g
n hc
=
b
3 1240 eV × nm g = 0.85 nm.
8cmc h E
2
n c hb
8 511 ´ 10 eV 4.7 eV
3
g
 399

54. The energy levels are given by En = n2h2/8mL2, where h is the Planck constant, m is
the mass of an electron, and L is the width of the well. The frequency of the light that will
excite the electron from the state with quantum number ni to the state with quantum
number nf is
DE h
f = =
h 8mL2
( n2f - ni2 )
and the wavelength of the light is
c 8mL2c
l= = .
(
f h n2f - ni2 )
We evaluate this expression for ni = 1 and nf = 2, 3, 4, and 5, in turn. We use h = 6.626 ´
10– 34 J · s, m = 9.109 ´ 10– 31kg, and L = 200 ´ 10– 12 m, and obtain the following results:

(a) 4.37 ´ 10– 8 m for nf = 2, (the longest wavelength).

(b) 1.65 ´ 10– 8 m for nf = 3, (the second longest wavelength).

(c) 8.77 ´ 10– 9 m for nf = 4, (the third longest wavelength).

400 CHAPTER 39

55. THINK The energy levels of an electron trapped in a regular corral with widths Lx
and Ly are given by Eq. 39-20:
h 2 é nx2 ny ù
2

Enx ,n y = ê + ú.
8m êë L2x L2y úû

EXPRESS With Lx = L and Ly = 2L, we have

E n x ,n y =
LM
h 2 nx2 n y
+
2
OP
=
h2
n
LM
2
+
n 2y OP
MN
8m L2x L2y PQ
8mL2
x
MN 4
.
PQ
Thus, in units of h2/8mL2, the energy levels are given by nx2 + ny2 / 4. The lowest five
levels are E1,1 = 1.25, E1,2 = 2.00, E1,3 = 3.25, E2,1 = 4.25, and E2,2 = E1,4 = 5.00. It is clear
that there are no other possible values for the energy less than 5.

The frequency of the light emitted or absorbed when the electron goes from an initial
state i to a final state f is f = (Ef – Ei)/h, and in units of h/8mL2 is simply the difference in
the values of nx2 + n2y / 4 for the two states. The possible frequencies are as follows:

0.75 (1, 2 ® 1,1) , 2.00 (1,3 ® 1,1) ,3.00 ( 2,1 ® 1,1) ,

3.75 ( 2, 2 ® 1,1) ,1.25 (1,3 ® 1, 2) ,2.25 ( 2,1 ® 1, 2 ) ,3.00 ( 2,2 ® 1,2 ) ,1.00 ( 2,1 ® 1,3) ,
1.75 ( 2, 2 ® 1,3) ,0.75 ( 2, 2 ® 2,1) ,

all in units of h/8mL2.

ANALYZE (a) From the above, we see that there are 8 different frequencies.

(b) The lowest frequency is, in units of h/8mL2, 0.75 (2, 2 ® 2,1).

(c) The second lowest frequency is, in units of h/8mL2, 1.00 (2, 1 ® 1,3).

(d) The third lowest frequency is, in units of h/8mL2, 1.25 (1, 3 ® 1,2).

(e) The highest frequency is, in units of h/8mL2, 3.75 (2, 2 ® 1,1).

(f) The second highest frequency is, in units of h/8mL2, 3.00 (2, 2 ® 1,2) or (2, 1 ® 1,1).

(g) The third highest frequency is, in units of h/8mL2, 2.25 (2, 1 ® 1,2).

LEARN In general, when the electron makes a transition from (nx, ny) to a higher level
(n¢x , n¢y ), the frequency of photon it emits or absorbs is given by
 401

DE En¢x , n¢y - Enx , ny h æ 2 n¢y ö h æ 2 ny ö

2 2

f = = = n
ç x ¢ + ÷ - n
ç x + ÷
h h 8mL2 çè 4 ÷ø 8mL2 çè 4 ÷ø
h é 2 ù
2 ê( x
n¢ - nx2 ) + ( n¢y2 - ny2 ) ú .
1
=
8mL ë 4 û