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 2m c c c2

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 8 Solutions to the Exercises in Quantum Mechanics I: The Fundamentals

For A = (Bz, 0, 0) and φ = −Ez we have

∂ψ 1 q q2
i = − 2 ∇ ψ + 2i Bzψ + B z ψ − qEzψ .
∂t 2m 2 2 2
z
c c2

2.4 What is the Schrödinger equation of a system of two particles of

masses m1 and m2 carrying charges q1 and q2 respectively with
1 2 1 2 q1 q2
H = p + p + and r12 = |r1 − r2 |?
2m1 1 2m2 2 r12

∂ψ
The Schrödinger equation i = Hψ becomes
∂t
∂ψ 2 2
q1 q2
i =− ∇12ψ − ∇ 2ψ + ψ,
∂t 2m1 2m2 2 r12
where

∂2 ∂2 ∂2
∇2i = + 2 + 2, i = 1, 2 .
∂x i
2
∂y i ∂z i

2.5 Starting from the Schrödinger equation for ψ, obtain the equation for
ψ∗.

The Schrödinger equation for ψ is

∂ψ 2
i =− ∇2 ψ + V (X, t)ψ .
∂t 2m

Taking complex conjugate of the above equation we get

∂ψ ∗ 2
−i =− ∇2 ψ ∗ + V ∗ (X, t)ψ ∗ .
∂t 2m

This is the Schrödinger equation for ψ ∗ .

2.6 If E1 and E2 are the eigenvalues and φ1 and φ2 are the eigenfunctions
of a Hamiltonian operator then find whether the energy corresponding
to the superposition state φ1 + φ2 is equal to E1 + E2 or not.

We have Hφ1 = E1 φ1 and Hφ2 = E2 φ2 . Then

H (φ1 + φ2 ) = Hφ1 + Hφ2

= E1 φ 1 + E2 φ2
= (E1 + E2 ) (φ1 + φ2 ) .

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 Schrödinger Equation and Wave Function 9

2
2.7 Express the Schrödinger equation − ∇2 + V (x, y, z) ψ(x, y, z) =
2m

Eψ(x, y, z) in the spherical polar coordinates defined by x = r sin θ cos φ,

y = r sin θ sin φ, z = r cos θ and in the parabolic coordinates defined by
ξ = r(1 − cos θ), η = r(1 + cos θ), φ = φ cos θ.

In spherical polar coordinates the Schrödinger equation is

2
1 ∂ 2 ∂ 1 ∂ ∂
− r + sin θ
2m r 2 ∂r ∂r r 2 sin θ ∂θ ∂θ
1 ∂2
+ + V (r, θ, φ) ψ(r, θ, φ) = Eψ(r, θ, φ) .
r 2 sin2 θ ∂φ2

In the parabolic coordinates the Schrödinger equation is

2
4 ∂ ∂ ∂ ∂ 1 ∂2
− ξ + η +
2m ξ + η ∂ξ ∂ξ ∂η ∂η ξη ∂φ2

+V (ξ, η, φ) ψ = Eψ .

2.8 Find the condition under which both ψ(X, t) and ψ ∗ (X, −t) will be the
solutions of the same time-dependent Schrödinger equation.

The Schrödinger equations for ψ(X, t) and ψ ∗ (X, −t) are given by
∂ψ 2
i = − ∇ 2 ψ + V (X, t)ψ ,
∂t 2m
∂ψ ∗ 2
2
i =
− ∇ ψ ∗ + V ∗ (X, −t)ψ
∂t 2m

respectively. The above two equations are identical if V (X, t) =

V ∗ (X, −t), that is if V is real and an even function of t.

2.9 What is the major difference between real and complex wave functions?

The probability current density J is given by

J= [ψ ∗ ∇ψ − ψ∇ψ ∗ ] .
2mi

If ψ is real then J = 0. If ψ is complex then J need not be zero.

2.10 What is the difference between the wave function ψ1 = ei(kx−ωt) and
ψ2 = ei(k·X−ωt) ?

ψ1 is a plane (probability)wave travelling along a one-dimensional line.

ψ2 is a three-dimensional (probability)wave.

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 10 Solutions to the Exercises in Quantum Mechanics I: The Fundamentals

2.11 Write the Hamiltonian of a photon.

For a photon H = E = mc2 = mcc = pc.

2.12 What is the physical meaning of �x� = 0?

ψ is symmetric or antisymmetric with respect to x = 0.

2.13 Write the operator forms of kinetic energy and angular momentum L =
r × p.

The operator form of kinetic energy mv 2 /2 is

1 p2 2
(K.E.)op = mv 2= = − ∇2 .
2 2m 2m

For L = r × p we have with r = ix + jy + kz

i j k
L = r×p = x y z
px py pz
= i (ypz − zpy ) + j (zpx − xpz ) + k (xpy − ypx ) .

The components of L are

∂ ∂ ∂ ∂
Lx = i −y +z =i z −y ,
∂z ∂y ∂y ∂z

∂ ∂ ∂ ∂
Ly = i −z +x =i x −z ,
∂x ∂z ∂z ∂x

∂ ∂ ∂ ∂
Lz = i −x +y =i y −x .
∂y ∂x ∂x ∂y

d
2.14 Consider the one-dimensional Schrödinger equation u(x) = − ln ψ(x).
dx
Obtain the Schrödinger equation under the change of variable
d
u(x) = − ln ψ(x).
dx

The general transformation is u = −ψx /ψ or ψx = −uψ. Then ψxx =

−ux ψ − uψx . Now, the Schrödinger equation is rewritten as (with λ =
2mE/ 2 and g = 2mV / 2 )

−ux ψ − uψx + (λ − g)ψ = 0 or − ux ψ + u2 ψ + (λ − g)ψ = 0 .

That is, ux − u2 − λ + g = 0.

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 Schrödinger Equation and Wave Function 11

2.15 Find the conditions to be satisfied by the functions f and g such that
under the transformation ψ = f (x)F (g(x)) the Schrödinger equation
ψxx + (E − V )ψ = 0 can be written as
Fgg + Q(g)Fg + R(g)F (g) = 0 . (2.1)
Then show that
2
1 Q2 g g
E − V = (g )2 R − Q − + . (2.2)
−
g
2 4 2g 2g

In terms of f and F the Schrödinger equation is written as

f F + 2f F + f F + (E − V )f F = 0 , (2.3)
where prime denotes differentiation with respect to x. Since F is F (g(x))
we have
F = Fg g , F = Fgg (g )2 + Fg g . (2.4)
Then Eq. (2.3) becomes
2f g f (E − V )
F =0. (2.5)
Fgg + + 2 Fg + 2f 2
+
gf g g g 2

Comparison of Eqs. (2.1) and (2.5) gives

2f g f E −V
Q= + 2 , R= + . (2.6)
gf g g 2f 2
g2

The conditions on f and g are given by Eqs. (2.6). From Eqs. (2.6) we
obtain
f gQ g
= − (2.7a)
f 2 2g

f
E −V = g 2R − . (2.7b)
f
From (2.7a) we find f /f and substituting it in (2.7b) we obtain
d f f f 2
= − . (2.8)
dx f f f2
That is,

f d f 2
= +f
f dx f f2
d gQ 2
= − g +
gQ
−
g
dx 2 2g 2 2g
2
1 g g 2 Q2 g
= Qg − + + . (2.9)
2 2g 4 2g

Substituting the above in Eq. (2.7b) we obtain the Eq. (2.2).

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 12 Solutions to the Exercises in Quantum Mechanics I: The Fundamentals

2.16 What are the effects of addition of a constant to a potential on the

time-independent Schrödinger equation and the energy levels?

The time-independent Schrödinger equation with the addition of a con-

stant α to a potential is given by
2
− ∇2 + V + α ψ n = E n ψ n .
2m
This can be rewritten as
2
− ∇2 + V ψn = (En − α) ψn = E �
n ψn ,
2m

where E �n = En − α. Therefore ψn remains the same but the energy

eigenvalues of the new system are En − α.

2.17 Which of the following wave functions are admissible in quantum me-
chanics? State the reasons.
2
(a) e−x . (b) sechx. (c) −x
√ e 2 . (d) tanhx. (e) sin x, 0 < x <2 2π. (f) sin x,
−∞ < x < ∞. (g) e −x . (h) tan x. (i) secx. (j) xe−x . (k) 1 − x2 ,
−1 < x < 1.

The conditions to be satisfied by a wave function are: (i) ψ should be

normalizable. (ii) It should be single-valued. (iii) It must be finite at
every point. (iv) It and its first partial derivatives must be continuous.
The functions (a), (b), (e), (j) and (k) satisfy all the above conditions
and hence they are admissible wave functions (verify).
The functions (c), (d), (f), (h), (i) are nonnormalizable. The function
(g) is multivalued. Therefore, they are not admissible wave functions.
2
/(2σ 2 ) .
2.18 Normalize the wave function ψ = N eikx−x
From the normalization condition we obtain
∞ ∞
2 √
1= ψ ∗ ψ dx = N 2 σ e−y dy = N 2 σ π .
−∞ −∞

√ 1/2
Thus N = 1/ (σ π ) .

2.19 Find the value of N for which the wave function ψ(x) = N for |x| < a
and 0 for |x| > a is normalized.
The normalization condition gives
a a
1 = ψ ∗ ψ dx = N 2 dx = N 2 x|a−a
−a −a
2
= 2aN .
√
Thus, N = 1/ 2a .

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 Schrödinger Equation and Wave Function 13

2.20 Normalize the wave function ψ = e−|x| sin αx. It is given that
∞
e sin αx dx = α /(1 + α ).
−x 2 2
0

The normalization condition gives

∞
1 = N2 e−2|x| sin2 αx dx
−∞
0 ∞
= N2 e2x sin2 αx dx + N 2 e−2x sin2 αx dx
−∞ 0

∞
= 2N 2 e−2x sin2 αx dx
0
∞
N 2 −2x ∞ N2
= − e |0 − e−x cos αx dx
2 2 0
∞
N2 N2
= − −e−x cos αx0 |∞ − α e−x sin αx dx
2 2 0

N2 N2 α3
= − 1−
2 2 1 + α2

N 2 α3
= .
2(1 + α2 )

That is, N = 2(1 + α2 )/α3 .

2.21 A particle of mass m moves in a one-dimensional box of length L with

origin as the centre. If the wave function of this particle is ψ(x) =
N x(1 − x2 ) for |x| < L/2 and 0 otherwise find the factor N .

N can be determined from normalization condition. We obtain

L/2
2
1 = N2 x2 1 − x2 dx
−L/2
L/2
= N2 x2 − 2x4 + x6 dx
−L/2

L3 L5 L7
= N2 − +
12 160 448

Thus,
−1/2
L3 L5 L7
N = − + .
12 160 448

If L is very small then N ≈ 12/L3 .

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 14 Solutions to the Exercises in Quantum Mechanics I: The Fundamentals

2.22 A quantum mechanical particle moving in one-dimension has the wave

function ψ(x) = cxe−|x|/b , −∞ < x < ∞ where c and b are constants
(b > 0). Find the probability that the position of the particle lies in the
region −∞ < x ≤ b.

First, we normalize the wave function. We obtain

∞
1 = ψ ∗ ψ dx
−∞
∞
= c2 x2 e−2|x|/b dx
−∞
0 ∞

= c2 x2 e2x/b dx + c2 x2 e−2x/b dx
−∞ 0

∞
= 2c2 x2 e−2x/b dx .
0

Substituting 2x/b = y in the integral, we get

∞
b 3 c2
1= y 2 e−y dy .
4 0

Integrating by parts we get

∞ ∞
b 3 c2 3 2 3 2
bc bc
1= ye−y dy = e−y dy = .
2 0 2 0 2

That is c2 = 2/b3 or c = 2/b3 . The probability P (−∞ < x ≤ b) is

b
P = ψ ∗ ψ dx
−∞
0 b
2
= x2 e2|x|/b dx + x2 e−2x/b dx
b3
−∞ 0
3 0 b
2 b
= − y 2 e−y dy + y 2 e−y dy
b3 8 ∞ 0
∞ b
1
= y 2 e−y dy + y 2 e−y dy
4 0 0

Integrating by parts we get

e−b 2
P =1− b + 2b + 2 .
4

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 Schrödinger Equation and Wave Function 15

2.23 What is the probability current density corresponding to ψ(x) = Ae−αx

where A and α are constants?

The probability current density is given by

J= [ψ ∗ ∇ψ − ψ∇ψ ∗ ] .
2mi

Since the given ψ is real, ψ ∗ = ψ,

J = [ψ∇ψ − ψ∇ψ] = 0 .
2mi

2.24 A free particle in one-dimension is in a state described by ψ =

A ei(px x−Et)/ + B e−i(px x+Et)/ where px and E are constants. Find
the probability current density.
J is given by

J = Im(ψ ∗ ∇ψ)
m
= Im A∗ e−i(px x−Et)/ + B ∗ ei(px x+Et)/
m
ipx
+ Be
−i(px x+Et)/
× Aei(px x−Et)/
px 2 2

= |A| − |B| .
m

2
2.25 If the wave function of a particle at t = 0 is ψ(x, 0) = N e−ikx−(x /2a 2)

calculate the probability density and current density.

First, we normalize the given wave function. We obtain

∞ ∞
√
ψ ∗ ψ dx = 2N 2 a e−y dy = N 2 a π .
2
1=
−∞ 0

That is N = (1/(a2 π))1/4 . The probability density is obtained as

1
P (x) = √ e−x /a .
2 2

a π

Then the current density is determined as

dψ dψ ∗
J (x) = ψ∗ −ψ
2mi dx dx
k 1 2 2

−x /a
= √ e
m a π
k
= P (x) .
m

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 16 Solutions to the Exercises in Quantum Mechanics I: The Fundamentals
1/2
1
e−x
2
√ /2σ 2
2.26 For the Gaussian wave function ψ(x) = calculate
σ π
the probability current density.

The probability current density is given by

dψ ∗
J = dψ −ψ .
2mi ψ∗ dx
dx
For any real ψ

dψ dψ ∗
ψ∗ −ψ
=0.
dx dx
Then J = 0. Therefore, for the real Gaussian function J = 0.
2 2
2.27 Verify whether the wave function ψ = N eikx−x /(2a ) satisfies the conti-
nuity equation or not.
∂ρ dJ
The continuity equation is given by + = 0. For the given function
∂t dx
∂ρ
ρ = ψ ∗ ψ = N 2 e−x /a and
2 2
= 0. Further
∂t

dψ
J = Im ψ dx
∗
m 2 2

= Im N 2 e−x /a
ik − x/a2
m

N 2 k −x2 /a2
= e .
m
Then
dJ N2 k 2 2
= −2 xe−x /a
.
dx ma2
2 2

Now the continuity equation becomes xe−x /a

= 0 which is true only if

x = 0. Hence, the given ψ does not satisfy the continuity equation.

2.28 The wave function of a linear harmonic oscillator with potential V =

mω 2 x2 /2 is ψ = xe−mωx /(2 ) . Find its energy.
2

The Schrödinger equation for a potential V is

2m
ψxx + 2
(E − V )ψ = 0 .

For the given potential and ψ the above equation becomes

−3mω m2 ω 2 3 2mE m2 ω 2 3
x+ 2
x + 2
x− 2
x =0.

From the above equation we get E = 3 ω/2.

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 Schrödinger Equation and Wave Function 17

2.29 If ψ = 1/L cos(πx/(2L)) for the system confined to the potential

V (x) = 0 for |x| < L and ∞ for |x| > L then calculate E.
The Schrödinger equation for the given system is
2m
ψxx + 2
Eψ = 0 .

Then

2 2
π 2 πx 2 π2

Eψ = − ψxx = √ cos = ψ.
2m 2m L 2L 2L 8mL2

2 π 2 /(8mL2 ).
Thus. E =
2.30 The wave function of a particle confined to a box of length L is
2/L sin(πx/L) in the region 0 < x < L and zero everywhere else. Cal-
culate the probability of finding the particle in the region 0 < x ≤ L/2.

We obtain
L/2
P (0 < x ≤ L/2) = ψ ∗ ψ dx
0

L/2
2 πx
= sin2 dx

L 0 L
L/2
1 2πx 1
= 1 − cos dx = .
L 0 L 2
2.31 Write the law of conservation of energy H = T + V in terms of expec-
tation values.
We write �H� = �T � + �V �.
0
2.32 Are the wave functions
1/2 1/2
1 r/a0 1 r r/(2a0 )
− a −
ψ1 = 0 e and ψ2 = 2− e
πa3 32πa3 0

of the electron in hydrogen atom orthogonal?

The orthogonality integral is calculated as
∞ ∞
r
ψ ψ dτ r2 e−3r/2a0 dr
∗
1 2 ∝ 2−
0 0 a0
∞ ∞
2 −y
∝ 6 y e dy − 2 y 3 e−y dy
0 0
∞ ∞
∝ 6 y 2 e−y dy − 6 y 2 e−y dy
0 0

= 0.
∞
Since ψ ∗1 ψ 2dτ = 0, the given two wave functions are orthogonal.
0

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 18 Solutions to the Exercises in Quantum Mechanics I: The Fundamentals

2.33 Find the potential corresponding to the following wave functions:

1 −x2 /2
(a) ψ = e , E = ω/2.
π 1/4

(b) ψ = A sin(πx/(2L)) for |x| < L and 0 for |x| > L, E = 2 π 2 /(8mL2 ).

(c) ψ = αxe−βx eiE/ .

(d) ψ = (mV0 / )e−kx for x > 0, (mV0 / )ekx for x < 0 and E =
−mV0 /(2 2 ), k 2 = mV0 / 2 .

(a) The eigenvalue equation Hψ = Eψ is

− 2 d2 ψ 2
+ V ψ = Eψ or Vψ= ψxx + Eψ .
2m dx2 2m
Substituting the given ψ and E in the above equation we get
2 2
d
Vψ= (−x)ψ + Eψ = −ψ + x2 ψ + Eψ .
2m dx 2m
Then
2 2
ω
V = −1 + x 2
+E = x −1 +
2
.
2m 2m 2

(b) For the given wave function we obtain

2
d π πx
Vψ = A cos + Eψ
2m dx 2L 2L
π
2 2
= − ψ + Eψ
8mL2
= −Eψ + Eψ
= 0.

Therefore, V (x) = 0 for |x| < L and ∞ for |x| > L.

(c) Using the given wave function we get

2 d −βx
Vψ = αeiE/ e − βx2 e−βx + Eψ
2m dx
2

= αeiE/ −βe−βx − 2βxe−βx + β 2 x2 e−βx + Eψ

2m
or
2
V αxe−βx eiE/ = αeiE/ −βe−βx − 2βxe−βx + β 2 x2 e−βx + Eψ .
2m

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 Schrödinger Equation and Wave Function 19
That is,
2
β
V = − − 2β + β 2 x + E .
2m x

(d) For the given wave function for x > 0

2 2
d
Vψ= (−kψ) + Eψ = k 2 ψ + Eψ .
2m dx 2m
k2 2
Then V = − 1 . Similarly, for x < 0 we obtain V =
2 m
k2 2
−1 .
2 m
2.34 A particle of mass m is confined in the infinite square-well potential V =
0 for 0 < x ≤ L and V = ∞ otherwise. It has the normalized stationary
state eigenfunctions φn (x) and eigenvalues En = n2 2 π 2 /(2mL2 ).√Its
wave function at time t = 0 is given by ψ(x, 0) = (φ1 (x) + φ2 (x))/ 2 .
What is the smallest positive time τ for which ψ(x, t) will be orthogonal
to ψ(x, 0)?

The wave function ψ(x, t) is

1
ψ(x, t) = √ φ1 e−iE1 t/ + φ2 e−iE2 t/ .
2

At t = τ the condition for ψ(x, 0) and ψ(x, t) to be orthogonal is

L
ψ ∗ (x, τ )ψ(x, 0) dx = 0 .
0

We get
L

φ∗1 e iE1 τ /
+ φ∗2 eiE2 τ / (φ1 + φ2 ) dx = 0 .
0

L
Since φ φ dx = δ we get eiE1 τ / + eiE2 τ / = 0. That is
0 m n mn

E1 τ E1 τ E2 τ E2 τ
cos + i sin + cos + i sin =0.

Equating the real and imaginary parts to zero separately we get

E1 τ E2 τ E1 τ E2 τ
cos = − cos , sin = − sin .

We rewrite the above conditions as

E1 τ π + E2 τ E1 τ π + E2 τ
cos = cos , sin = sin .

Thus, τ = π/(E1 − E2 ). Since E2 > E1 we write τ = π/(E2 − E1 ).

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 20 Solutions to the Exercises in Quantum Mechanics I: The Fundamentals
2.35 Show that �xpx + px x� is real.

Consider �px x�. We obtain

∞
�px x� = ψ ∗ px xψ dx
−∞

∞
= (p†x ψ)∗ xψ dx
−∞
∞ ∗

= px ψx∗ ψ ∗ dx
−∞
∞ ∗
= ψ ∗ xpx ψ dx
−∞

= �xpx �∗ .
Now, �xpx + px x� = �xpx � + �px x� = �xpx � + �xpx �∗ = 2Re�xpx �. Thus
�xpx + px x� is real.

2.36 Show that �An � = �A �n in its eigenstates.

Let Aψ = αψ. Then we obtain

∞
�An � = ψ ∗ An ψ dτ

−∞
∞
= ψ A Aψ dτ
∗ n−1
−∞
∞
= α ψ ∗ An−1 ψ dτ
−∞
∞
= αn ψ ∗ ψ dτ
−∞
= αn .
∞ ∞
We find �A� = ψ ∗ Aψ dτ = α ψ ∗ ψ dτ = α. Hence, �An � = αn =
−∞ −∞
n

�A� .
√
2.37 Calculate �p2 � for ψ = e−k|x| .
x k
We obtain
∞ ∞ 2
d −k|x|
�p
x � =
2
ψ ∗ p2x ψ dx = − 2
e−k|x| e dx .
dx2
−∞ −∞

The above equation can be rewritten as

0 2 ∞ 2
d kx −kx d −kx
x�p � −
2 2 kx
= k e e dx + e e dx .
dx2 dx2
−∞ 0

K24365_SM_Cover.indd 34 13/11/14 6:56 PM

 Schrödinger Equation and Wave Function 21
Then we obtain
0 ∞
x�p � = − k
2 2 3
e2kx dx + e−2kx dx = − 2 k 2 .
−∞ 0

2.38 A particle of mass m in the one-dimensional energy well V (x) = 0 for

0 ≤ x ≤ L and ∞ otherwise is in a state whose wave function is given
by ψ(x) = N x(L − x) where N is the normalization constant. Determine
�E� in this state.

The normalization condition gives

L
N 2L 5
1 = N2 x2 (L − x)2 dx = .

0 30
That is, N = 30/L5 . Next,
L
�E� = ψ ∗ Hψ dx
0

L 2
d2
= ψ −
0 2m dx2 ψ dx
2 L

= N2 xL − x2 dx
m 0

5 2
= .
mL2
d 2 2 i
2.39 Show that �x � = �xpx � − .
dt m m

∞
�x2 � is given by �x2 � = ψ ∗ x2 ψ dx. Then
−∞
∞
d 2 d
�x � = ψ ∗ x 2 ψ dx
dt dt −∞

∞ ∞
∂ψ ∗ ∂ψ
= x2 ψ dx + ψ ∗2x dx .
−∞ ∂t −∞ ∂t
∂ψ ∂ψ ∗
Using the Schrödinger equation for and we get
∂t ∂t

∞
d 2 1 p2xψ ∗ ∗ 2
�x � = − +Vψ x ψdx
dt i −∞ 2m
∞
1 p2
∗ 2
+ ψ x x
ψ+Vψ dx
i −∞ 2m

i =
2m
K24365_SM_Cover.indd 35 13/11/14 6:56 PM
∞
i∞
ψ ∗ p2 x2 ψ x dx
−∞ −
2m ψ ∗ x2 p2 ψ
dx . x
−∞

K24365_SM_Cover.indd 35 13/11/14 6:56 PM

 22 Solutions to the Exercises in Quantum Mechanics I: The Fundamentals

Expanding the first integral we obtain

∞
d 2 i 2 2 2
�x � = ψ ∗ 2pψpx x + ψp x dx
dt 2m −∞
∞
i
= ψ ∗ −4i xpx ψ + 2ψ(−i )2 dx
2m −∞
2 i

2
= �xpx � − .
m m
d 2 2
2.40 Show that �x2 � = �p2 � + �xF �.
x
dt2 m2 m

d 2 i
We have � x2 � = �xpx � − . Then
dt m m

d2 2 2 d
�x � = �xpx �
dt2 m dt

∞
2 d
= ψ ∗ (xpx )ψ dx
m dt −∞
2 ∞ ∂ψ ∗ 2 ∞
∂ψ
= xpx ψ dx + ψ ∗ xpx dx .
m −∞ ∂t m −∞ ∂t

Using the Schrödinger equation

∞ ∞
d2 2 i 2 2i
�x � = px ψ ∗ xpx ψ dx + V ψ ∗ xpx ψ dx
dt2 m2 −∞ m −∞

∞ ∞
i 3 2i
− ψ ∗ xpx ψ dx − ψ ∗ xpx (V ψ) dx
m2 −∞ m −∞

∞
i
= ψ 2 px (px xpx ψ + xp2 ψ) − xp3 ψ dx
x x
m2 −∞
∞
2i dV
− ψ ∗ xψ −i dx .
m −∞ dx

Substituting F = −dV /dx we get

∞
d2 2 i 2 2
�x � = ψ ∗ 2px xpx ψ dx + �xF �
dt 2 m2 −∞ m
∞
2i 2

= ψ ∗ (−i )p2x ψ dx + �xF �

m2 −∞ m
2 2

K24365_SM_Cover.indd 36 13/11/14 6:56 PM

 = �p2x � + �xF � .
m2 m

K24365_SM_Cover.indd 36 13/11/14 6:56 PM

 Schrödinger Equation and Wave Function 23
d
2.41 Show that �p 2
� = �2F px + px F �.
dt x
∞
By definition �p
x �=
2 ψ ∗ p2x ψdτ . Then
−∞
∞ ∞
d 2 ∂ψ ∗ 2 2 ∂ψ

�px � = px ψ dτ + ψ ∗ px dτ .
dt −∞ ∂t −∞ ∂t

Using the Schrödinger equation we obtain

∞
d 2 1 p2xψ ∗ ∗ 2

�px � = − +Vψ px ψ dτ
dt i −∞ 2m
∞
1 p2 ψ
+ ψ ∗ p2x x
+Vψ dτ .
i −∞ 2m
That is,

∞ ∞
d 2 i 2 i 2
∗
�px � = V ψ px ψ dτ − ψ ∗ px (V ψ) dτ
dt −∞ −∞

∞ ∞
i
= − 2 ψ ∗ px V px ψ dτ + ψ ∗ p2 V ψdτ
−∞ −∞ x

∞ ∞
i i
= −2 (−i ) ψ ∗ ∇V px ψ dτ − (−i ) ψ ∗ (px ∇V )ψ dτ
−∞ −∞

∞ ∞
= 2 ψ ∗ F p x ψ dτ + ψ ∗ p x F ψdτ
−∞ −∞
�2F px + px F
=
�.
d 1
2.42 Show that �px x� �p 2
� + �xF �.
dt m x
=

The expectation value of px x is

∞
�px x� = ψ ∗ px xψ dx
−∞
∞ ∞

= −i ψ ∗ ψ dx + ψ ∗ xpx ψ dx
−∞ −∞
∞

= −i + ψ ∗ xpx ψ dx .
−∞

Now
�px x� =
d dt

K24365_SM_Cover.indd 37 13/11/14 6:56 PM

 ∞
d
dt ψ ∗ xpx
−∞
ψ dx
∞ ∞
∂ψ ∗ ∂ψ
= xpx ψ dx + ψ ∗ xp x dx .
−∞ ∂t −∞ ∂t

K24365_SM_Cover.indd 37 13/11/14 6:56 PM

 24 Solutions to the Exercises in Quantum Mechanics I: The Fundamentals

We have
∂ψ p2x ∂ψ ∗ p2x
i = ψ+Vψ , −i = ψ∗ + V ψ∗ .
∂t 2m ∂t 2m

Using these two equations for ∂ψ/∂t and ∂ψ ∗ /∂t we get

∞ ∞
d i 2 ∗ i
�px x� = px ψ xpx ψ dx + V ψ ∗ xpx ψ dx
dt 2m −∞ −∞

∞ ∞
i 3 i
− ψ ∗ xpx ψ dx − ψ ∗ xpx (V ψ) dx
2m −∞ −∞

∞ ∞
i i
= ψ ∗ p2x (xpx ψ) dx − ψ ∗ xp3x ψ dx
2m −∞ 2m −∞

∞
+ ψ ∗ xψF dx .
−∞

Then

∞ ∞
d i 2 i 3
∗ ∗
�px x� = ψ px (xpx ψ) dx − ψ xpx ψ dx + �xF �
dt 2m −∞ 2m −∞
∞
i
= ψ ∗ px xp2x ψ dx + �xF �
2m −∞

∞
1
= ψ ∗ p2x ψ dx + �xF �
m −∞
1 2
= �p � + �xF � .
m x
d 2 d 2
2.43 For a free particle show that �p � = 0 and �xpx + px x� = �p2x �.
dt x dt m

We have the result

d 1 d 2
�px x� = �px2 � + �xF � , �p � = �2F px + px F � .
dt m dt x
For a free particle F = 0 and hence

d 1 d 2
�px x� = �px2 � , �p � = 0 .
dt m dt x

Consider [x, px ] = xpx − px x = i . From this we write

xpx − px x + px x − px x = i
xpx + px x − 2px x = i
xpx + px x = i + 2px x .

K24365_SM_Cover.indd 38 13/11/14 6:56 PM

 Then
d d 2 2
=2
�xpx + px x� �px x� = �px � .
dt dt m

K24365_SM_Cover.indd 38 13/11/14 6:56 PM

 Schrödinger Equation and Wave Function 25

2.44 φ1 and φ2 are the only eigenfunctions of a system belonging to the energy
eigenvalues E0 and −E0 respectively. In a measurement of the energy
of the system, �E� is found to be E0 /2. Find the wave function of
the system.

The wave function of the system is ψ = C1 φ1 + C2 φ2 , C 21 + C 22 = 1.

Further

�E� = 1 C 2 E1 +2 C 2 E2
= C12 E0 − C22 E0
= E0 C 21 − C 22 .

Since �E� = E0 /2 we get√1 C −2 C = 1/2. Solving 1C +2C = 1 and

2 2 2 2
2 2
C C = 1/2 we get C = 3/2 and C = 1/2 . Then
1 − 2 1 2
√
3 1
ψ= φ1 + φ2 .
2 2

2.45 The H of a charged particle in uniform electric and magnetic fields

1
is given by H = (p − eA)2 − eE0 k.k where A = B0 (−y, x, 0)/2.
2m
Both electric field E and magnetic field B are applied along the z-
d 1
direction. Applying Ehrenfest’s theorem, show that �r� �p − eA�
dt m
=

d e
and �p − eA� = eE0 k �p − eA� × ∇ × A.
dt m
+
1 2
∇ × A is obtained as ∇ × A = B0 k. H is (p − eA) − eE0 . Now,
2m
d
consider �x�. We obtain
dt

∞
d ∂ψ ∗ ∞
∂ψ
�x� = xψ dx + ψ∗x dx
dt −∞ ∂t ∂t
−∞

= ∞ ∞
1 1
− Hψ ∗ xψ dx + ψ ∗ xHψ dx
i −∞ i −∞

1
= �[x, H]� .
i

K24365_SM_Cover.indd 39 13/11/14 6:56 PM

 26 Solutions to the Exercises in Quantum Mechanics I: The Fundamentals

Next, we find
1
[x, H] = x, (p − eA) · (p − eA) + eE0
2m
1 1
= x, px2 + x, e2 A2
2m 2m
1 1
− [x, p · eA] − [x, eA · p] + [x, eE0 ]
2m 2m
1 1 1
= x, px2 − (i eAx ) − (i eAx )
2m 2m 2m
i i
= px − eAx .
m m
Therefore,

d 1 i eAx 1
�x� = px − i = m (px − eAx ) .
dt i m m

Hence,
d 1
�r� = �p − eA� .
dt m
Next,

d2 d d d
�r� = �F� = m �r� =
dt2 dt dt
�p − eA�
dt
1
= �[p − eA, H]�
i

We obtain with v = dr/dt, B = ∇ × A

e
�F� = eE + �v × B − B ×
2m
v�
e
= eE + [(p − eA) × B − B × (p − eA)]
2m
e
= eE + m [(p − eA) × ∇ × A] .

Hence,

d e
�p − eA� = �F� = eE0 k + (p − eA) × ∇ × A .
dt m

2.46 A particle of mass m enclosed in a one-dimensional box of length L

such that 0 < x < L, has energy eigenfunctions φn (x) = A sin(nπx/L),
n = 1, 2, · · · and En = n2 π 2 2 /(2mL2 ). At t = 0, the particle has the
wave function ψ(x) = B sin(2πx/L) cos(πx/L) where B is a constant.
(i) If the energy of the particle is measured at t = 0, what are the

K24365_SM_Cover.indd 40 13/11/14 6:56 PM

 Schrödinger Equation and Wave Function 27

possible results of the measurement? (ii) What is the expectation value

of energy?

(i) The wave function can be written as a combination of eigenfunctions

as
2πx πx
ψ = B sin cos
L L
B πx 3πx
= sin + sin
2 L L
B
= (φ1 + φ3 ) .
2
That is, the system can have only two eigenstates φ1 and φ3√each with
probability B 2 /4. Further, (B 2 /4) + (B 2 /4) = 1 gives B = 2. There-

fore,
1
ψ = √ (φ1 + φ3 ) .
2
If the energy is measured then one may get the energy as E1 with the
probability 1/2 and E3 with probability 1/2.
(ii) We obtain

1 5π 2 2
�E� = C 2 E1 + C 2 E3 = (E1 + E3 ) = .
1 3
2 2mL2

2.47 Given the normalized ground state wave function of hydrogen atom
ψ100 = 1/(πa30)1/2 e−r/a0 find the expectation value of its z-coordinate.
We obtain
∞ π 2π
1 − 2r/a0 2
�z� = e zr dr sin θdθ dφ .
πa2
0 0 0 0

Substituting z = r cos θ we get

∞ π 2π
1
�z� = r3 e−2r/a0 sin θ cos θ dr dθ dφ
πa3
0 0 0 0
∞
1 π 3 −2r/a

= − 3 cos 2θ|0
r e 0
dr
2a0 0

= 0.

K24365_SM_Cover.indd 41 13/11/14 6:56 PM

 28 Solutions to the Exercises in Quantum Mechanics I: The Fundamentals

2.48 If H φn (x) = En φn (x) find the expectation value of the Hamilto-

nian operator H in the normalized superposition state ψ(x, t) =
∞
n=0 Cn φn (x) e−iEn t/ .
We obtain

E = ψ|H|ψ
∞
= C n∗ Cn ei(En −En )t/
φ∗n Hφn dx

n n −∞
∞
= Cn Cn∗ ei(En −En )t/ φ∗n En φn dx

n n −∞

∗ i(En −En )t/

= Cn Cn En δnn
e
n n

= |Cn |2 En .
n

√
2.49 Consider a system in a state ψ = (φ1 + φ2 )/ 2 where φ1 and φ2 are

orthonormal eigenfunctions with the eigenvalues E1 and E2 respectively.

What is the probability of finding the system in the energy E1 ? What
is E ?
√
The probability of finding the system with energy E1 is (1/ 2)2 = 1/2.
Next
2
1 1 1
E = |Cn |2 En = E1 + E2 = (E1 + E2 ) .
n=1
2 2 2

2.50 Consider a spherically symmetric potential energy function given by

V (r) = 0, for 0 < r < a and ∞ for r > a. Given the solu-
sin kr cos kr
tion ψ(r) = A +B where k = (2mE/ 2 )1/2 satisfying the
r r
Schrödinger equation, obtain the corresponding eigenvalues by applying
proper boundary conditions.

As r → 0, ψ must be finite. The condition limr→0 ψ(r) = finite sets

sin kr
B = 0. So ψ(r) = A . At r = a we require ψ = 0. This gives
r
sin ka = 0. That is, ka = nπ, n = 1, 2, · · · . Hence, the energy eigenvalues
are given by
2 2
kn n2 2 π 2
En = = .
2m 2ma2

K24365_SM_Cover.indd 42 13/11/14 6:56 PM

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