Indian Institute of Technology Bombay

PHY-403 Quantum Mechanics-I 8.09.2023

Assignment 5

Notes:

1. Some problems will be discussed on 14.09.2023.

2. Please make sure that you do the assignment by yourself. You can con-
sult your classmates and seniors and ensure you understand the concept.
However, do not copy assignments from others.

3. During the tutorial session, TA will randomly ask a student to come to the
board to solve tutorial problems.

1. Consider the Ammonia molecule discussed in the class. As discussed in

the class, we can define the two sets of states of the Ammonia molecule:
{|1i, |2i} and {|+i, |−i}. We know that state |1i is not an energy eigenstate
and is a superposition of two energy states (|+i and |−i) with different
energies.

(a) Calculate the uncertainty in the energy of a molecule in this state.

1/2
∆E = E 2 − hEi2

(b) Re-express the time evolution of the total state vector |Ψ(t)i in terms
of the uncertainty ∆E How long do we have to wait before the state
of the molecule changes?

2. Triatomic molecule

A molecule is made up of three identical atoms at the corners of an equi-

lateral triangle as shown in the figure above. We consider its ion to be

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 made by adding one electron with some amplitude on each site. Suppose
the matrix element of the Hamiltonian for the electron on any two adjacent
sites i, j is hi|H|ji = −V for i 6= j.
Calculate the energy eigenvalues and eigenvectors.

3. Tetra-atomic molecule
In the class we discussed the Tetra-atomic molecule like Ammonia. Let us
assume that the energy of the electron at each site is given by 0 and the
transition rates between sites connected by a solid line are all equal to V /h̄.
Using a basis set |1i, |2i, |3i, |4i for each site, the Hamiltonian is given by
the matrix:  
0 V 0 0
 V 0 V V 
H=  0 V 0 0 


0 V 0 0
Find the eigenvalues and eigenvectors. Are any of these states degenerate?

4. In the class we discussed Periodic chains of N = 6 atoms. Instead, consider

a linear chain of 6 equispaced atoms. Label the kets as |ni, n = 1, . . . , N so
that the state of an electron at time t is given by:
N
X
|ψ(t)i = cn (t)|ni.
n=1

The Hamiltonian is given by:

N
X
H= {0 |nihn| + V [|nihn + 1| + |n + 1ihn|]} .
n=1

which differs from periodic case only by the range of n. Assume the follow-
ing finite Fourier sine transform:
N
1 X
|ni = √ sin(πnk/(N + 1))|ki,
f
N + 1 k=1
N
f=√ 1
X
|ki sin(πnk/(N + 1))|ni,
N + 1 n=1

(a) What does the above Sine transform mean for |0i, |7i, |0i
f and |7i.
f

(b) Do the states |ki

f satisfy the completeness relation?
PN
(c) Obtain n=1 [|nihn + 1| + |n + 1ihn|] in the Fourier basis states.
(d) Write the Hamiltonian in the Fourier basis states.

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 (e) Are there any degenerate eigenvalues?

5. The Hamiltonian operator for a two-state system is given by

H = a(|1ih1| − |2ih2| + |1ih2| + |2ih1|),

where a is a number with the dimension of energy. Find the energy eigen-
values and the corresponding energy eigenkets (as linear combinations of
|1i and |2i ).

6. In a given basis, a two state system has the following Hamiltonian

 
0 1
H=E
1 0

At t = 0, in the same basis, the system is in the following state:

 
0
ψ(0) =
1

(a) Find Ψ(t).

(b) What is the probability to observe the system in the same state at
t=T?
(c) What is the probability that the system is in the state
 
1
0

at t = T ?

7. Consider a two-state system |1i, |2i. The Hamiltonian matrix in the or-
thonormal basis {|1i, |2i} is a Hermitian 2 × 2 matrix that can be written
in terms of the three Pauli matrices
     
0 1 0 −i 1 0
σ̂1 =  σ̂2 =  σ̂3 = 
1 0 i 0 0 −1

and the unit matrix as

1
H= (H0 + H · σ) .
2
In terms of the matrix elements Hij = hi|H|ji of the original Hamiltonian,
the components of the vector H are
∗ ∗
H1 = H12 + H12 , H2 = i (H12 − H12 ), H3 = H11 − H22

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 (a) Consider the density matrix ρ(t) = |ψ(t)ihψ(t)| corresponding to the
state |ψ(t)i of the system. Show that it satisfies the time-evolution
equation
dρ i
= − [H, ρ]
dt h̄
(b) If the density matrix can be written in the following matrix form
1
ρ = (1 + Φ · σ)
2
Identify Φ.
(c) Show that time-evolution equation for ρ can equivalently be written
as:
dΦ 1
= H×Φ
dt h̄
Is this motion periodic? Solve for Ψ(t).
(d) Calculate the return probability

P(t) = |hψ(0) | ψ(t)i|2 = hψ(0) | ψ(t)ihψ(t) | ψ(0)i = hψ(0)|ρ(t)|ψ(0)i

8. For a certain system, the operator corresponding to the physical quantity

A does not commute with the Hamiltonian. It has eigenvalue a1 and a2 ,
corresponding to eigenfunctions
√ √
φ1 = (u1 + u2 ) / 2, φ2 = (u1 − u2 ) 2,

where u1 and u2 are eigenfunctions of the Hamiltonian with eigenvalues

E1 and E2 . If the system is in the state ψ = φ1 at time t = 0, find the
expectation value of A at time t.

9. Let  
E0 0 A
 0 E1 0 
A 0 E0
be the matrix representation of the Hamiltonian for a three-state system
with basis states |1i, |2i, and |3i.

(a) If the state of the system at time t = 0 is |ψ(0)i = |2i, what is |ψ(t)i
?
(b) If the state of the system at time t = 0 is |ψ(0)i = |3i, what is |ψ(t)i
?

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10. The matrix representation of the Hamiltonian for a photon propagating
along the optic axis (taken to be the z axis) of a quartz crystal using the
linear polarization states |xi and |yi as a basis is given by
 
0 −iE0
Ĥ −→
|xi−|yi basis iE0 0

(a) What are the eigenstates and eigenvalues of the Hamiltonian?

(b) A photon enters the crystal linearly polarized in the x direction, that
is, |ψ(0)i = |xi. What is the |ψ(t)i, the state of the photon at time
t ? Express your answer in the |xi − |yi basis. What is happening to
the polarization of the photon as it travels through the crystal?

11. Statistical Matrix: In the class we showed that two-state systems oscillate
between two states. We derived this via the Schrödinger equation. One can
also obtain the same using von Neumann equation:

∂ ρ̂(t) ih i
= − Ĥ, ρ̂ (1)
∂t h̄
(a) Write down the Hamiltonian operator interms of |T i and |Bi, i. .e,



Ĥ = Ē − ∆ |BihB| + Ē + ∆ |T ihT | + V (|BihT | + |T ihB|) (2)

(b) For an arbitrary state vector

|Ψi = c1 (t) |Bi + c2 (t) |T i (3)

Show that the statistical matrix is given by

ρ̂ = ρBB BihB| + ρT T |T ihT | + ρBT |BihT | + ρT B |T ihB| (4)

(c) What is the relation between ρBT and ρT B ? Show that

ρBB + ρT T = 1 (5)

(d) Using Eq. (1), show that

d
ih̄ ρ = V (ρBT − ρT B ) (6)
dt T T
d
ih̄ ρBB = −V (ρBT − ρT B ) (7)
dt
d
ih̄ ρT B = ∆ρBT + V (1 − 2ρBB ) (8)
dt

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(e) These are coupled differential equations, instead of solving them head-
on, let us rewrite the above variables in terms of P, J and I:
P = (ρBT + ρT B ) (9)
J = i (ρBT − ρT B ) (10)
I = 1 − 2ρBB (11)
Show that Eqs. (6 - 8), can be rewritten as
dI
h̄ = −2 J , V (12)
dt
dJ
h̄ = ∆P + 2I V (13)
dt
dP
h̄ = −∆ J (14)
dt
(f) Write down the above equations for Ammonia Molecule. What does
I and J physically correspond to?
Hint: What values I can take?
(g) Define vectors:
S = (P, J, I) Ω = (−2V, 0, ∆) /h̄ (15)
Show that Eqs. (12 - 14) can be combined in to single differential
equation as
dS
=Ω×S (16)
dt
What physical situation does this equation correspond to?
Hint: Look at Sections (5.8) and (5.9) of Goldstein, Classical Mechan-
ics.
(h) Show that S has a fixed length and
P 2 + J2 + I2 = 1 (17)
(i) Using the above equation and Eqs. (12 - 14), show that
d2 J
h̄2 + Γ2 J = 0 where Γ2 = ∆2 + 4V 2 (18)
dt2
(j) With the inital condition that I(t = 0) = 1, J(t = 0) = P (t = 0) = 1,
show that
 
2V Γt
J(t) = sin (19)
Γ h̄
   
2V ∆ Γt
P (t) = cos −1 (20)
Γ h̄
8V 2
 
Γt
I(t) = 1 − sin (21)
Γ 2h̄

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 Compare these expressions with the ones obtained in the class.

12. Two-level system with dynamical coupling

The dynamics of the two level system are much richer in the event that
the coupling between the states is time-dependent and has important for
applications in a variety of different areas, including NMR, laser physics.
Let us consider the following Hamiltonian
 
Ē − ∆ V (t)
Ĥ = (22)
V ∗ (t) Ē + ∆

(a) Using the approach on Problem 1 (in this assigment), obtain the dif-
ferential equation for I, J and P .
(b) Assume V (t) = V0 exp(iωt) and solve the differential equations.
(c) Assume that at initial time I(t = 0) = −1, J(t = 0) = P (t = 0) = 0.
Show that
1 (2V /h̄)2  p
2 2

ρBB = 1 − sin (ω − ω0 ) + (2V /h̄) t (23)
2 (ω − ω0 )2 + (2V /h̄)2