Quantum Mechanics-I (PH5130/PH51010)

Homework Set 0∗

August 6, 2024

1.
Consider a non-relativistic particle of mass M in one dimension, confined in a potential
that vanishes for −a ≤ x ≤ a, and becomes infinite at x = ±a, so that the wave function
must vanish at x = ±a.
A. Find the energy values of states with definite energy, and the corresponding normalized
wave functions.
B. Suppose that the particle is placed in a state with a wave function proportional to
a2 − x2 If the energy of the particle is measured, what is the probability that the particle
will be found in the state of lowest energy?

Solution: A. The energy eigenstates (wave-function) obeys the form of the Schrödinger
equation in the interval x ∈ [−a, a]
ℏ2 d2 ψ
− = Eψ,
2m dx2
or,
d2 ψ 2 m E
+ ψ = 0,
dx2 ℏ2
for an energy eigenvalue E with the boundary condition, ψ (x = ±a) = 0. For E < 0,
the general solution is of the form,

ψ(x) = Aκ eκx + Bκ e−κx ,

where as usual,
2mE
κ2 ≡ − .
ℏ2
Enforcing the boundary condition leads to,

Aκ eκ a + Bκ e−κ a = 0 = Aκ e−κ a + Bκ eκ a

The only solution to these two conditions (since the exponential function does not
vanish for finite real arguments) is,

Aκ = Bκ = 0∀κ.
∗
All problems are taken from Ch. 1 of Weinberg’s text.

1
Thus there are no negative energy eigenvalues. Similarly one can rule out zero eigen-
value, E = 0. In this case, the general solution is of the form,

ψ = Ax + B

and enforcing the boundary conditions lead to,

A a + B = 0 = −A a + B,

the only solution to which (since a is nonzero) is,

A = B = 0.

Finally we consider positive energy eigenvalues, E > 0. The general form of the
solution is,
ψ = Ak cos kx + Bk sin kx
where as usual we define k (to be strictly positive to avoid double-counting) via,
2mE
k2 ≡ .
ℏ2
Demanding ψ (x = ±a) = 0 implies,

Ak cos k a + Bk sin k a = 0 = Ak cos k a − Bk sin k a,

or, equivalently,
Ak cos k a = 0 = Bk sin k a.
Since sine and cosine functions can never vanishing simultaneously at the same value
of the argument, there are two separate solutions these equations,

Bk = 0, cos k a = 0, OR, Ak = 0, sin k a = 0.

(NB: These two classes of solutions correspond to even and odd parity eigenstates
since they are purely even and odd functions of x respectively). The first (even parity)
condition leads to,
 
1
ke a = n − π,
2
 
1 π
⇒ ke = n −
2 a

while the second condition (odd parity) leads to,

ko a = nπ
nπ
⇒ ka =
a
where n is a positive integer (n = 1, 2, . . .). Both these solutions can be combined into
a single equation,
π
k=N , N = 1, 2, . . .
2a
2
with odd N corresponding to even parity states while even N corresponding to odd
parity states. The energy eigenvalues are then given by,
ℏ2 k 2 ℏ2 π 2
E= = N 2.
2m 8 m a2
The eigenfunctions are,

ψe (x) = Ake cos ke x, ψo (x) = Bk0 sin k0 x.

Finally, invoking the normalization condition,

ˆ a
dx |ψ(x)|2 = 1,
−a

we obtain
1
|Ake |2 = |Bko |2 = .
a
Choosing both to be real without loss of generality,
r
1
Ake = Bko = .
a
Thus, the normalized energy eigenfunctions are,
 q
1
 cos N2aπ x , N = 1, 3, . . .
ψN (x) = qa .
1 N πx

a
sin 2a
, N = 2, 4, . . .

B. The state is given by the wave-function,


C (a2 − x2 ) , x ∈ [−a, a]
ψ(x) = ,
0, |x| > a

where C is the (real positive) normalization constant. First we determine C from,

ˆ a r
2 15 1
dx |ψ(x)| = 1 ⇒ C = .
−a 16 a5/2
Thus, the normalized wave-function reads,
r
x2
 
15
ψ(x) = 1− 2 .
16 a a
Evidently this is an even function, we can expand this wave-function in a basis of
purely even parity energy eigenstates,
X
ψ(x) = cN ψN (x), N = 1, 3, . . .
N
r
X 1 N πx
= cN cos , N = 1, 3, . . .
N
a 2a

3
 The goal is to compute the probability of the particle being in the lowest energy
eigenstate, N = 1, which is given by

P1 = |c1 |2 .

To this end we first extract the expansion coefficient c1 using the

ˆ a
c1 = dx ψ1∗ (x) ψ(x)
−a
r ˆ
1 15 a π x
a2 − x 2


= 3 dx cos
a 16 −a 2a
√
8 15
= .
π3
The probability of the particle being found in the lowest energy eigenstate (ground
state) is, then,
960
P1 = 6 ≈ 0.998555.
π
2.
Consider a non-relativistic particle of mass M in three dimensions, described by a Hamilto-
nian
P2 M ω02 2
H= + X
2M 2
A. Find the energy values of states with definite energy, and the number of states for each
energy.
B. Find the rate at which a state of next-to-lowest energy decays by photon emission into
the state of lowest energy.

(Hint: You can express the Hamiltonian as a sum of three Hamiltonians for one-
dimensional oscillators, and use the results given in Section 1.4 for the energy levels and
x-matrix elements for one-dimensional oscillators.)

Solution: The Hamiltonian is a sum of three one-dimensional single harmonic oscil-

lator Hamiltonians, namely H1 , H2 , H3

H = H1 + H2 + H3

where,

ℏ2 ∂ 2 1 ℏ2 ∂ 2 1 ℏ2 ∂ 2 1
H1 = − 2
+ M ω02 x2 , H2 = − 2
+ M ω02 y 2 , H3 = − 2
+ M ω02 z 2
2m ∂x 2 2m ∂y 2 2m ∂z 2
The (normalized) eigenstates/eigenfunctions of H1 , H2 , H3 are respectively are all fa-
miliar from the knowledge of the one-dimensional harmonic oscillator (Sec. 1.4 of
Weinberg),
 
1
H1 ψn1 (x) = En1 ψn1 (x), En1 = n1 + ω0 , n1 = 0, 1, 2, . . . , (1)
2

4
  
1
H2 ψn2 (y) = En2 ψn2 (y), En2 = n2 + ω0 , n2 = 0, 1, 2, . . . , (2)
2
and,  
1
H3 ψn3 (z) = En3 ψn3 (z), En3 = n3 + ω0 , n3 = 0, 1, 2, . . . . (3)
2
Since H1 , H2 , H3, , H, all commute among themselves:

[Hi , Hj ] = [H, Hi ] = 0, i, j = 1, 2, 3,

there exist simultaneous eigenfunctions of H1 , H2 , H3, , H, say ψn1 ,n2 ,n3 (x, y, z) which
satisfy,
Hi ψn1 ,n2 ,n3 (x, y, z) = Eni ψn1 ,n2 ,n3 (x, y, z), i = 1, 2, 3. (4)
H ψn1 ,n2 ,n3 (x, y, z) = En1 ,n2 ,n3 ψn1 ,n2 ,n3 (x, y, z) En1 ,n2 ,n3 = En1 + En2 + En3 . (5)
Comparing the set of individual equations (1)-(3) with the simultaneous/joint eigen-
value equations (4), (5), it becomes evident that

ψn1 ,n2 ,n3 (x, y, z) = ψn1 (x) ψn1 (x) ψn1 (x).

If we define a column vector for the quantum number, n = (n1 , n2 , n3 ), and the usual
position 3-vector x = (x, y, z) one can shorten the notation ψn1 ,n2 ,n3 (x, y, z) = ψn (x)
and have the eigenfunctions,

H ψn (x) = En ψn (x)

corresponding to eigenvalue,
 
3
E n = n1 + n2 + n3 + ℏ ω0 .
2

One can introduce the principal quantum number or principal level number, n ≡
n1 + n2 + n3 , and the energy eigenvalues are then given by,
 
3
En = n + ℏ ω0 , n = 0, 1, 2, . . . .
2

Evidently for a given principal quantum number n there are multiple triplets of indi-
vidual quantum numbers n’s, i.e. the energy levels have degeneracy or multiplicity.
Let’s compute the degeneracy of the state with principal quantum number n. Here n1
can assume n + 1 different values, i.e. n1 can range from 0 to n. Then, for a fixed n and
corresponding to every fixed (allowable) value of n1 , the second quantum number n2
can assume n−n1 +1 values ranging from 0 to n−n1 . Finally, for a fixed value of n, n1 ,
and n2 , the third quantum number n3 gets fixed to a single value n3 = (n − n1 − n2 ).

5
Thus, the degeneracy/multiplicity of states of principal quantum number n is,
n n−n
X X1
Ω(n) = 1
n1 =0 n2 =0
X n
= (n − n1 + 1)
n1 =0
n
X n
X
= (n + 1) 1− n1
n1 =0 n1 =0
n(n + 1)
= (n + 1)2 −
2
(n + 1) (n + 2)
= . (6)
2
Alternatively:
The degeneracy of the system can be evaluated using more abstract method with the
help of combinatorics (Methods of counting).
n1 + n2 + n3 = n (7)
Let’s solve for this problem at hand by considering another analogical problem of
counting. As, it can easily be observed from Eq (7) that the degeneracy of the system
can be counted by counting how many ways ‘n’ identical balls can be distributed among
three boxes.
Let’s consider a box partitioned into three sections using two identical partitions and
the ‘n’ number of identical balls can be arranged among these sections. The number
of ways this can be done is the answer of our problem.
The solution is,
(n + 3 − 1)! (n + 2)! (n + 1)(n + 2)
Ω(n) = = = (8)
(3 − 1)!n! 2!n! 2
Here, ‘n’ is the number of balls, ‘3’ is the number of boxes, ‘2’ is the number of
partitions required to create ‘3’ boxes.
[Check: For the ground state, n = 0, there is only one state, i.e. one-fold degeneracy
since all three quantum numbers must be set to zero. Indeed plugging in n = 0 in the
formula (6), we get Ω(0) = 1. For the first excited state i.e., n = 1 the degeneracy is
3-fold where one of the three quantum numbers is set to 1 while the other two are set
to 0. Indeed plugging in n = 1 in the formula (6), we obtain Ω(1) = 3. Finally for the
second excited state, i.e. n = 2, one has 6-fold degerancy: One can have either one
of the quantum numbers to be 2 while the other two set to 0 in 3 ways, and, one can
have two of the quantum numbers to be 1 while the third equal to 0 in 3 ways. Again,
plugging in n = 2 in the formula (6), we obtain Ω(2) = 6.]

B. Referring to Eq. (1.4.5) of Weinberg’s text, the rate of transition from n = 1

state to n = 0 is given by (in Gaussian units),
4e2 3 2 4e2 3
A01 = 3
ω01 |[x 01 ]| = 3
ω01 |[x01 ]|2
3c ℏ cℏ
6
 where
E1 − E0
ω01 = = ω0 ,
ℏ
and referring to Eq. (1.4.15) of Weinberg’s text,
r
−i ω0 t ℏ
[x01 ] = e .
2 me ω0
Thus, we have the emission rate,
2e2 ω02
A01 = .
c3 me

3.
Suppose the photon had three polarization states rather than two. What difference would
that make in the relations between Einstein’s A and B coefficients?

Solution: Since the number of polarizations is now 3 instead of 2, Eq. (1.1.3) of Wein-
berg’s text for the number of normal modes in a radiation filled (cubical) cavity with
frequencies in the range (v, ν + dν) will be,

N (ν) dν = 3 × 4π |n|2 d |n| = 12π (L/c)3 ν 2 dν,

which will change the Planck distribution formula Eq. (1.1.5) to

12 π h ν 3 dν
ρ(ν, T ) = .
c3 exp( h ν/ ) − 1
kB T

Using this in the relation between the Einstein A and B coefficients, second part of
Eq. (1.2.16) we obtain,
3
12 πh νnm
Anm = 3
n
Bm .
c
(simple change in the numerical coefficient/pre-factor, 12 instead of 8).

4.
Show that the solution ψ(x, t) of the time-dependent Schrödinger equation for a particle in
2
a real potential has the property that ∂|ψ|
∂t
is the divergence of a three-vector.

Solution: The time-independent Schrödinger equation can be put in the form,

ℏ2 2
 
∂ψ i
=− − ∇ ψ+V ψ .
∂t ℏ 2m
Taking complex conjugate of both sides we obtain,
∂ψ ∗ ℏ2 2 ∗
 
i ∗
= − ∇ ψ +V ψ .
∂t ℏ 2m

7
Using these two we compute the

∂ |ψ|2 ∂ψ ∂ψ ∗
= ψ∗ +ψ
∂t ∂t ∂t
2
ℏ2
   
i ℏ ∗ 2 2
 i 2 ∗ 2
=− − ψ ∇ ψ +V |ψ| +

− V |ψ|
ψ∇ ψ +  
ℏ 2m ℏ 2m
iℏ
ψ ∗ ∇2 ψ − ψ∇2 ψ ∗


=
2m
iℏ
= ∇ · (ψ ∗ ∇ψ − ψ∇ψ ∗ )
2m
= ∇ · j,

where the three-vector,j is given by

iℏ
j= (ψ ∗ ∇ψ − ψ∇ψ ∗ ) ,
2m
which is the probability current-density three-vector (up to a “−” sign).