Solution:

E = }! = 2 jqe j (87)
r s
2E 2 (2 jqe j)
v= = = 8:387 105 m/s
me me
h h h
= = = = 0:8673 nm
p me v me (8:387 105 )
2 2
k= = = 7:244 109 m 1
0:8673 10 9
9 2jqe j
so, (z; t) = 200eikz ei!t = 200ei(7:244 10 )z e i( } )t ;

and
i} @ @
J (z; t) = b
z (z; t) (z; t) (z; t)(z; t) (88)
2me @z @z
i} 9 2jqe j @ 9 2jqe j
= b
z 200e i(7:244 10 )z ei( } )t 200ei(7:244 10 )z e i( } )t
2me @z
9 2jqe j @ 9 2jqe j
200ei(7:244 10 )z e i( } )t 200e i(7:244 10 )z ei( } )t (89)
@z
=b
z 3:355 1010 A/m.

4 Problems Chapter 4: Free and Con…ned Electrons

4.1. Write down the wavefunction (z; t) for a 3 eV electron in an in…nite space, travelling along the
positive z axis. Assume that the electron has only kinetic energy. Plug your answer into Schrödinger’s
time-dependent equation to verify that it is a solution.
Solution:

E = }! = 3 jqe j (90)
r s
2E 2 (3 jqe j)
v= = = 1:027 106 m/s
me me
h h h
== = = 0:7082 nm
p me v me (1:027 106 )
2 2
k= = = 8:872 109 m 1
0:7082 10 9
r
2me
or, use (4.5), k = 3 jqe j = 8:87 109 (91)
}2
9 3jqe j
so, (z; t) = Aeikz e i!t = Aei(8:872 10 )z e i( } )t

@ (z; t) }2 d 2
i} = +V (z; t) : (92)
@t 2m dz 2

4.2. Determine the wavefunction (z; t) for a 3 eV electron in an in…nite space, travelling along the z
axis at a velocity of 105 m/s. Determine the particle’s potential energy, and plug your answer into
Schrödinger’s time-dependent equation to verify that it is a solution.

13
 Solution:
1 1 2
E = }! = 3 jqe j = V + EKE = V + me v 2 = V + me 105 (93)
2 2
1 5 2
! V = 3 jqe j me 10 = 2:972 eV
2
h h h
= = = = 7:274 nm
p me v me 105
2 2
k= = = 8:638 108 m 1
7:274 10 9
8 3jqe j
so, (z; t) = Aeikz ei!t = Aei(8:638 10 )z e i( } )t
Plugging into Schrödinger’s time-dependent equation we obtain
@ (z; t) }2 d 2
i} = +V (z; t) (94)
@t 2m dz 2
d 108 )z
3jqe j }2 @ 2 8 3jqe j
i} ei(8:638 e i( } )t = 2
ei(8:638 10 )z e i( } )t + V
dt 2me @z
V = 2:971 eV (95)
4.3. For classical light the expression
c= f (96)
holds, where c is the speed of light, f is the frequency, and is the wavelength. This expression also
holds for quantized light (i.e., photons), where the classical wavelength is the same as the de Broglie
wavelength. Does the expression
v = f; (97)
where v is velocity, hold for electrons if is the de Broglie wavelength and f = !=2 is the frequency,
such that E = }!? Assume that the electrons have only kinetic energy.
Solution: No.
1
h E E mv 2 v
v= f= = = 2 = (98)
p }2 p mv 2
The velocity obtained from v = f is the phase velocity, which is not the meaningful velocity. For an
electron with kinetic energy E one needs to use the classical expression for kinetic energy, E = (1=2) mv 2
to obtain v. More generally, one needs to us the concept of group velocity,
@! @ (E=})
vg = = : (99)
@k @k
4.4. Consider an electron in a room of size 10 10 10 m3 . Assume that within the room potential energy
is zero, and that the walls and ceilings of the room are perfect (so that the electron can not escape from
the room). If the electron’s energy is approximately 5 eV, what is the state index n2 = n2x + n2y + n2z ?
What is the approximate energy di¤erence E2;1;1 E1;1;1 ?
Solution:
}2 2
En = n2 + n2y + n2z = 5 jqe j (100)
2me L2 x
r
5 jqe j 2me 102
!n= = 3:65 1010 :
}2 2
What is the approximate energy di¤erence E2;1;1 E1;1;1 ?
}2 2
E2;1;1 E1;1;1 = 22 + 12 + 12 12 + 12 + 12 (101)
2me 102
39 20
= 1:8 10 J=1:124 10 eV
Therefore, the states essentially form a continuum.

14
 9 9 9
4.5. Repeat problem 4.4 for an electron con…ned to a nanoscale space, 10 10 10 m3 .
Solution:
}2 2
En = n2 + n2y + n2z = 5 jqe j (102)
2me L2 x
s
2
5 jqe j 2me (10 9 )
!n= = 3:65:
}2 2

What is the approximate energy di¤erence E2;1;1 E1;1;1 ?

}2 2
E2;1;1 E1;1;1 = 22 + 12 + 12 12 + 12 + 12 (103)
2me (10 9 )2
19
= 1:8 10 J = 1:12 eV

These states will be easily observed to be discrete.

4.6. Consider an electron having kinetic energy 2:5 eV. What size space does the electron need to be con…ned
to in order to observe clear energy discretization? Repeat for a proton having the same kinetic energy.
Solution:
s
1 2 (2:5 jqe j)
E = me v 2 = 2:5 jqe j ! v = = 9:378 105 m/s (104)
2 me
p = me v = me 9:378 105 = 8:543 10 25
kg m/s
h h
= = = 0:776 nm
p 8:543 10 25
In order to observe clear energy discretization, the space must be on the order of = 0:776 nm, or
smaller.
For a proton having the same kinetic energy,
s
1 2 (2:5 jqe j)
E = mp v 2 = 2:5 jqe j ! v = = 21885 m/s (105)
2 mp
p = mp v = mp (21885) = 3:661 10 23 kg m/s
h h
= = = 0:0181 nm,
p 3:661 10 23
and thus the space must be on the order of 0:0181 nm.
4.7. Consider a 44 kg object (perhaps your desk) in a typical room with dimensions 10 10 m2 . Assume
that within the room, potential energy is zero, and that the walls of the room are perfect (so that the
room can be modeled as an in…nitely deep potential well).

(a) If the desk is in the ground state, what is the velocity of the desk?
Solution:
1 }2 2 }2 2
E= mv 2 = En = (1 + 1 + 1) = (1 + 1 + 1) = 3:7 10 71
(106)
2 2mL2 2 (44) 102
r
2 (3:7 10 71 )
v= = 1:3 10 36 m/s
44

(b) If the desk is moving at 0:01 m/s, what is the desk’s quantum state (i.e., what is the state index
n)?

15
 Solution:
1 1 2 }2 2 2
E= mv 2 = (44) (:01) = 0:0022 = n (107)
2 s 2 2mL2
2
(0:0022) 2 (44) (10)
!n= = 1:3 1034 :
}2 2

4.8. Consider the one-dimensional, in…nite square well existing from 0 x L. The wavefunction for a
particle con…ned to the well is (4.34),
1=2
2 n iEn t=}
(x; t) = sin x e : (108)
L L
If the particle is in the ground state, determine the probability, as a function of time, that the particle
will be in the right half of the well (i.e., from L=2 x L).
Solution: From (3.6),
Z L
P = (x; t) (x; t) dx (109)
L=2
Z L 1=2 1=2
2 n iEn t=} 2 n
= sin x e sin x eiEn t=} dx
L=2 L L L L
Z L
2 1
= sin2 x dx = :
L L=2 L 2

4.9. Consider an electron in the …rst excited state (n = 2) of an in…nitely-high square well of length 2:3
nm. Assuming zero potential energy in the well, determine the electron’s velocity.
Solution: We have
}2 n 2
En = (110)
2me L
2
}2 2
E2 = 9
= 0:284 eV. (111)
jqe j 2me 2:3 10
Then, r
2me E2
k= ; (112)
}2
and r
p }k } 2me (0:284) jqe j
ve = = = = 3:161 105 m/s. (113)
me me me }2
4.10. Consider an electron con…ned to an in…nite potential well having length 2 nm. What wavelength
photons will be emitted from transitions between the lowest three energy levels
Solution:
}2 n 2
En = ; (114)
2me L
so that
2
}2
E3 E1 = 9
32 12 = 0:752 eV, (115)
jqe j 2me 2 10
2
}2
E3 E2 = 9
32 22 = 0:470 eV,
jqe j 2me 2 10
2
}2
E2 E1 = 9
22 12 = 0:282 eV,
jqe j 2me 2 10

16
4.11. Consider the one-dimensional, in…nite square well existing from 0 x L. Recall that the energy
eigenfunctions for a particle con…ned to the well are (4.31),
1=2
2 n
n (x) = sin x ; (116)
L L

n = 1; 2; 3; :::. Now, assume that the particle state is

(x) = A (x (L x)) ; (117)

such that (0) = (L) = 0.

(a) Determine A such that the particle’s state function is suitably normalized.
Solution:
Z L
2
A2 (x (L x)) dx = 1 (118)
0
r
1 30
A2 L5 = 1 ! A = :
30 L5

(b) Expand (x) in the energy eigenfunctions, i.e., use orthogonality to …nd cn such that
1
X
(x) = A (x (L x)) = cn n (x) (119)
n=1

Solution:
Z L Z L
r
30
m (x) (x) dx = m (x) (x (L x)) dx (120)
0 0 L5
Z L 1
X 1
X Z L
= m (x) cn n (x) dx = cn m (x) n (x) dx = cm
0 n=1 n=1 0
Z L Z L 1=2
r
2 n 30
cn = n (x) (x) dx = sin x (x (L x)) dx
0 0 L L L5
r r Z
2 30 L n
= 5
sin x (x (L x)) dx
L L 0 L
s s
p 1 p 1 n sin n + 2 cos n 2
= 2 30 L3
L L5 n3 3
p 1 cos n
= 4 15 :
n3 3

(c) Determine the probability of measuring energy En , and use this result to determine the probability
of measuring E1 through E6 .

17
 Solution:
Z L
2

P (En ) = (x) n (x) dx (121)

0
Z 1
L X
2
p 1 2
2 cos n
= cm m (x) n (x) dx = jcn j = 4 15
0 m=1
n3 3
16(60)
= n6 6 ; n odd
0; n even
16 (60) 2
P (E1 ) = jc1 j = = 0:99856 = 99:8%
16 6
2 16 (60)
P (E3 ) = jc3 j = 6 6 = 0:00137 = 0:137%
3
2 16 (60)
P (E5 ) = jc5 j = 6 6 = 6:391 10 5 = 0:0064%
5
4.12. Repeat problem 4.11 if the particle state is
2
(x) = A (x (L x)) : (122)

(a) Determine A such that the particle’s state function is suitably normalized.
Solution:
Z L
4
A2 (x (L x)) dx = 1
0
r
2 1 9 630
A L =1!A= :
630 L9

(b) Expand (x) in the energy eigenfunctions, i.e., use orthogonality to …nd cn such that
1
X
2
(x) = A (x (L x)) = cn n (x) (123)
n=1

Solution:
Z L Z L 1=2
r
2 n 630 2
m (x) dx = sin x (x (L x)) dx (124)
0 0 L L L9
1
X Z L
= cn m (x) n (x) dx
n=1 0

Z L 1=2
r
2 n 630 2
cn = sin x (x (L x)) dx (125)
0 L L L9
r Z L
1260 n 2
= sin x (x (L x)) dx
L10 0 L
r
1260 1
= 24L5 24L5 cos n 2 2
L5 n2 + 2 2
L5 n2 cos n
L10 5 n5
(
0;
q n = 0; 2; 4; :::
= 1260 1 5 2 5 2
L10 5 n5 48L 4 L n ; n = 1; 3; 5; :::

18
 (c) Determine the probability of measuring energy En , and use this result to determine the probability
of measuring E1 through E6 .
Solution:
Z L
2

P (En ) = (x) n (x) dx (126)

0
Z 1
L X
2
2
= cm m (x) n (x) dx = jcn j
0 m=1
1 2 2 2
1260 5 n5 48 4 n ; n odd
=
0; n even
2
2 1 2 2
P (E1 ) = jc1 j = 1260 5 15
48 4 1 = 0:9770 = 97:7%
2
2 1 2 2
P (E3 ) = jc3 j = 1260 5 35
48 4 3 = 0:0215 = 2:15%
2
2 1 2 2
P (E5 ) = jc5 j = 1260 5 55
48 4 5 = 0:00122 = 0:122%

4.13. Consider the one-dimensional, in…nite square well existing from 0 x L. If nine electrons are in the
well, what is the ground state energy of the system?
Solution: Using
}2 n 2
En = ; (127)
2me L
then for nine electrons, since two electrons can be in the same state (one of each spin), the n = 1; 2; 3; 4
states are …lled, and the 9th electron is in the n = 5 state. Therefore, the ground state energy of the
system is

2E1 + 2E2 + 2E3 + 2E4 + E5 (128)

2 2
}
= 2 12 + 22 + 32 + 42 + 52
2me L
2
}2 1 31:963
= 85 9
= eV
2me L 10 jqe j L2

where L is in nm.
4.14. Consider a one-dimensional quantum well of length L = 10 nm containing 11 non-interacting electrons.
Determine the chemical potential of the system.
Solution: With two electrons per state, N = 10 electrons and N = 12 electrons will have energy

Et (10) = 2E1 + 2E2 + 2E3 + 2E4 + 2E5 ; (129)

Et (12) = 2E1 + 2E2 + 2E3 + 2E4 + 2E5 + 2E6 (130)

Then,
2 2
Et (12) Et (10) }2 6 }2 6
= = E6 = = 9
= 0:135 eV:
2 2me L 2me jqe j 10 10

4.15. Apply boundary conditions (4.81) to the symmetric form of (4.78) (i.e., set C = 0 in (4.78)) for the
…nite rectangular potential energy well considered in Section 4.5.1 to show that the wavefunction (4.82)
results, where (4.83) must be satis…ed.

19
4.16. Repeat problem 4.15 for the antisymmetric form of (4.78) (i.e., with D = 0), showing that (4.84)
results, where the wavenumbers must obey (4.85).
4.17. Comparing energy levels in one-dimensional quantum wells, for an in…nite-height well of width 2L
energy states are given by (4.35) with L replaced by 2L,

}2 n 2
En = ; (131)
2me 2L
and for a …nite-height well of width 2L the symmetric states are given by a numerical solution of (4.83),

k2 tan (k2 L) = k1 : (132)

Assume that L = 2 nm, and compute E1 and E3 (the second symmetric state) for the in…nite-height
well. Then compare it with the corresponding values obtained from the numerical solution of (132) for
the …nite-height well. (You will need to use a numerical root-solver.) For the …nite-height well, assume
barrier heights V0 = 1000; 100; 10; 1; 0:5, and 0:2 eV. Make a table comparing the in…nite-height and
…nite-height results (with percent errors), and comment on the appropriateness, at least for low energy
states, of the much simpler in…nite well model for reasonable barrier heights, such as V0 = 0:5 eV.
Solution. For the in…nite-height well,
2
}2
E1 = 9)
= 0:0235 eV (133)
jqe j 2me 2 (2 10
2
}2 3
E3 = 9)
= 0:21152 eV. (134)
jqe j 2me 2 (2 10

For the …nite-height well,

2me E 2me (V0 E)

k2 tan (k2 L) = k1 ; k22 = 2
; k12 = (135)
} }2

r r ! r
2me E 2me E 2me (V0 E)
tan L = (136)
}2 }2 }2
r r ! r
2me E jqe j 2me E jqe j 9 2me ((V0 ) jqe j E jqe j)
2
tan 2
2 10 = 0: (137)
} } }2

The table below shows that the simple in…nite-height well is a reasonable model as a …rst approximation,
and gives an order-of-magnitude estimate, although the percent error is probably too large to provide
a quantitative model, especially for low barrier heights.
state E1 state E3
…nite-height …nite-height
V0 Enum erical %Error V0 Enum erical %Error
1000 0:02336 0:62 1000 0:21022 0:62
100 0:02305 1:96 100 0:20745 1:96
10 0:02212 6:27 10 0:19900 6:23
1 0:01950 20:54 1 0:17459 21:15
0:5 0:01812 29:70 0:5 0:16084 31:51
0:2 0:01576 49:13 0:2 0:13414 57:68
4.18. For a 1s electron in the ground state of hydrogen, determine the expectation value of energy.
Solution: Since
1 2 r
iE1 t=}
100 =p 3=2
e a0
e ; (138)
4 a0

20
 then, from (3.116)
Z 2 Z Z 1
@
hEi = (r; t) i} (r; t) r2 sin drd d (139)
0 0 0 @t
!2 Z Z Z
2 1
1 2 r @ r
= 3=2
e a0
eiE1 t=} i} e a0
e iE1 t=} 2
r sin drd d
4 a0 0 0 0 @t
!2 Z Z 1
1 2 2r
= 3=2
2 (E1 ) e a0
r2 sin drd = E1 :
4 a0 0 0

4.19. For an electron in the (n; l; m) = (2; 0; 0) state of hydrogen, determine the expectation value of position.
Solution: Since
1 1 r r

200 =p 2 e 2a0
; (140)
4 (2a0 )3=2 a0
then, from (3.112)
Z 2 Z Z 1
hri = (r; t) r (r; t) r2 sin drd d (141)
0 0 0
Z ! !
1
1 1 r r 1 1 r r
= p 2 e 2a0
(r) p 2 e 2a0
r2 dr
0 4 (2a0 )3=2 a0 4 (2a0 )3=2 a0
Z 1
1 r r r r
= 3 2 e 2a0
2 e 2a0
r3 dr
(2a0 ) 0 a 0 a0
1 1
= 3 48a50 = 6a0 :
(2a0 ) a0

4.20. Repeat problem 4.19 for an electron in the (n; l; m) = (2; 1; 0) state of hydrogen.
Solution:
r
r r1 3
2;1;0 = p e cos ; (142)
2a0
3=2 a 4
3 (2a0 ) 0
Z 2 Z Z 1
hri = (r; t) r (r; t) r2 sin drd d
0 0 0
Z Z Z r !2
2 1
r1 r 3
= p 3=2
e 2a0 cos r3 sin drd d
0 0 0 3 (2a0 ) a0 4
Z 2 Z Z r !2
1 r r 3
= d sin cos2 d p 3=2 a
e 2a0 r3 dr
0 0 3 (2a0 ) 0 4
4 1
= 120a50 = 5a0 :
3 32 a40

4.21. For an electron in the (nx ; ny ) = (1; 1) subband of a metallic quantum wire having Lx = Ly = 1 nm,
if the total energy is 1 eV, what is the electron’s longitudinal (i.e., z directed) group velocity?
Solution: From (4.133),
!
2 2
}2 2 nx ny }2 2
E= + + k (143)
2me Lx Ly 2me z
!
2 2
}2 2 1 1 }2
= + + k2
jqe j 2me 1 10 9 1 10 9 jqe j 2me z
= En + Econt = 1

21
 En = 0:7521, so Econt = E En = 10:7521 = 0:2479. Using E = }!,
r
}2 2 0:2479 jqe j 2me
0:2479 = k ! kz = = 2:551 109 (144)
jqe j 2me z }2
}2 2
k = }!
2me z
@! } }
(vg )z = = 2kz = 2 2:551 109 = 2:953 105 m/s.
@kz 2me 2me

4.22. A 3 eV electron is to be con…ned in a square quantum dot of side L. What should L be in order for
the electron’s energy levels to be well-quantized?
Solution: From (2.14),
h h h h
e = = = q = q = 0:708 nm; (145)
p me v 2E
me me 3jqe j
me 2 m e

and we need L e.

5 Problems Chapter 5: Electrons Subject to a Periodic Potential

–Band Theory of Solids
5.1. To gain an appreciation of the important role of surface e¤ects at the nanoscale, consider building up
a material out of bcc unit cells. (See Section 5.1). For one bcc cube, there would be 9 atoms, 8 on
the outside and one interior, as depicted on p. 134. If we constrain ourselves to only consider cubes
of material, the next largest cube would consist of 8 bcc unit cells, and so on. If one unit cell is 0:5
nm, how long should the material’s side be in order for there to be more interior atoms then surface
atoms?
Solution:
# unit cells in the cube Surface Atoms Interior Atoms Ratio (S/I)
1 8 1 8
23 = 8 26 9 2:9
33 = 27 56 35 1:6
43 = 64 98 91 1:1
53 = 125 152 189 0:8
so that we need 53 unit cells, leading to a material cube having side length 5 (0:5) = 2:5 nm.
5.2. Consider the Kronig-Penney model of a material with a1 = a2 = 5 Å and V0 = 0:5 eV. Determine
numerically the starting and ending energies of the …rst allowed band.
Solution: From
2 2
cos kT = cos ( a) cosh (b ) sin ( a) sinh (b ) ; (146)
2
if 0 < E < V0 , and
2 2
+
cos kT = cos ( a) cos (b ) sin ( a) sin (b ) ; (147)
2
if E > V0 . Then, for 0 < E < V0 the plot is Band edge energy occurs when cos kT is 1. It is found
numerically that cos kT = 1 when E = 0:459, cos kT = 0 when E = 0:300, and cos kT = 1 when
E = 0:217. Therefore, the band edges are at E = 0:217 eV and E = 0:459 eV.
5.3. Use the equation of motion (5.34) to show that the period of Bloch oscillation for a one-dimensional
crystal having lattice period a is
h
= : (148)
eEa

22