Quantum Tutorial Part I (CML101) (Semester I, 2024-2025)

1. Given  = d/dx and Ê = x2, show (a) Â2f(x) ≠ [Âf(x)]2 and (b) ÂÊf(x) ≠ ÊÂf(x) for arbitrary f(x).
2. Identify which of the following functions are eigenfunctions of the operators d/dx and d2/dx2: (a) eikx (b) cos
kx (c) k (d) kx (e) e–ax2. Give the corresponding eigenvalue where appropriate.
3. Find the eigenvalue in the following cases:
 (operator) f(x) Eigenvalue
d2 2 cos x
dx
d exp(it)
dt
2
d d
2
2 3 exp(x)
dx dx
 x 2 exp(6 y )
y

2 2 2
4. Show that (cos ax )(cos by )(cos cz ) is an eigenfunction of the operator  2    which is known
x 2 y 2 z 2
as the Laplacian Operator.
5. Write out the operator for Â2 for  =
d2 d d2 d
(a) 2
(b) x (c) 2
 2x 1
dx dx dx dx

6. Find the eigenfunctions of the operator d .

dx
7. In algebra it can be easily shown that (P + Q)(P – Q) = P 2 – Q2. What is the value of (P + Q)(P – Q) if P and
Q are operators? Under what conditions will this result be equal to P 2 – Q2?
8. (a) Find [d/dx, x], [z3, d/dz], [d2/dx2, ax2 + bx + c], and [a, a#] where a = (x + ip)/√2 and a# = (x – ip)/√2. (b)
Determine whether the operators SQR and SQRT commute.

 
9. Evaluate the commutator Aˆ , Bˆ , where  and B̂ are given below:

 B̂
________________________________________
d d
(a) x x
dx dx

d2 d
(b) x  x2
dx 2 dx
10. Normalize the following wavefunctions to unity:
(a) sin(nπx/L) for the range 0 ≤ x ≤ L.
(b) c, a constant in the range –L ≤ x ≤ L.

11. Prove that if (x) is a solution to the Schrödinger equation, then any constant times (x) is also a solution.
12. Which of the following candidates for wavefunctions are normalizable over the indicated intervals?
Normalize those that can be normalized.


(a) exp  x
2

2
   x 2  y 2 
(-, ) (b) ex (0, ) (c) exp(i) (0, 2) (d) xex (0, ) (e) exp 
 2
 (x,y: 0, )


13. Write down the Schrödinger equation for the following systems: (a) a particle of mass m in a cubical box of
side a; (b) a particle of mass m in a spherical box of radius a; (c) a particle of mass m moving on the x-axis
subjected to a force directed towards the origin, of magnitude proportional to the distance from the origin; (d) an
electron moving in the presence of a nuclear charge +Ze; (e) two electrons moving in the presence of a fixed
nucleus of charge +Ze
1 1 3i 2
14. The wave function for a system can be written as  ( x)  1 ( x)  2 ( x)  3 ( x) with 1 ( x) , 2 ( x)
2 4 4
and 3 ( x) being normalized eigenfunctions of the kinetic energy operator with eigenvalues E 1, 3E1 and 7E1
respectively. (a) Verify that (x) is normalized. (b) What are the possible values of KE you will obtain in
identically prepared systems. (c) What is the probability of measuring each of these eigenvalues? (d) What is the
average value of kinetic energy that you would obtain from a large number of measurements.
𝒙𝟐 ⁄𝟐𝒂𝟐
15. Suppose that a vibrating atom is described by the wavefunction 𝝍 = 𝑵𝒙𝒆 . Where is the most
probable location of the atom?
16. Consider a particle whose normalized wave function is

𝜓(𝑥) = 2𝛼√𝛼𝑥𝑒 𝑥>0

𝜓(𝑥) = 0 𝑥<0
(a) For what value of x does P(x) peak?
(b) Calculate 〈𝑥〉 and 〈𝑥 〉.
(c) What is the probability that the particle is found between x = 0 and 𝑥 = .

21.

Which of the wavefunctions shown in the figure above are well behaved? Give reasons for your answer.
Particle in a box
22. (a) Calculate the energy levels for n = 1, 2, and 3 for an electron in an infinite potential well of width 0.25
nm. (b) If an electron makes a transition from n = 2 to n =1 what will be the wavelength of the emitted radiation.
23. What is the probability of finding a particle in a 1-D box of length L: (a) in the right half of the box (b) in the
central third of the box and (c) between x = 0 and x = L/n when it is in the n-th state? Does this probability
y 1
depend on the quantum number labeling the state of the particle? Useful Integral:  sin 2 (by)dy   sin(2by )
2 4b
24. Find the expectation values of x, x2, p, p2 for the ground state and the first excited state of a particle in a one-
dimensional box.
25. (i) To a crude first approximation, a  electron in linear polyene may be considered to behave as a particle in
a one-dimensional box. The polyene in β- carotene contains 22 conjugated C atoms and the average internuclear
distance is 140 pm. Each state upto n = 11 is occupied by two electrons. Calculate (a) the separation energy
between the ground state and the first excited state in which one electron occupies the state with n = 12 and (b)
The frequency of the radiation required to produce a transition between these two states.
(ii) When β- carotene is oxidized, it breaks into half and forms two molecules of retinal (vitamin A) which is
a precursor to the pigment in the retina responsible for vision. The conjugated system for retinal consists of 11 C
atoms and one O atom. In the ground state of retinal, each level upto n = 6 is occupied by 2 electrons. Treating
everything else to be similar repeat calculations for parts (a) and (b) of the previous problem keeping in mind that
in this case the first excited state has one electron in the n = 7 state.
p2
26. Consider a particle of mass m in a 1D box of length a. Its average energy is given by E  . Using the
2m
2
uncertainty principle show that the energy must be at least as large as  because  x , the uncertainty in x,
8ma 2
cannot be larger than a.
27. Set up the problem of a particle in a box with its walls located at –L and +L. Show that the energies are
equal to those of a box with walls located at 0 and 2L. Show however that the wavefunctions are not the same.
Comment on the results thus obtained by you.
28. A particle with mass m moves in a 3D box with edges Lx = L, Ly = 2L, and, Lz = 4L. Find the energies of the
ten lowest states. Which ones are degenerate?
29. Consider a particle in a 1D box defined by V(x) =0, a > x > 0 and V(x) = , x  a, x  0. Explain whether the
following functions are acceptable wavefunctions for this particle or not:
(a) A cos(nx/a) (b) B (x+x2) (c) C x3(x-a) (d) D/sin(nx/a)
x
30. The function  ( x)  Ax[1  ] is an acceptable wavefunction for the particle in the one dimensional infinite
a
depth box of length a. Calculate the normalization constant A and the expectation values x and x 2 .

31. Find the average position of a particle in a 3D box of sides a, b, c.

32. Show that a particle in a box of length L satisfies the uncertainty principle.

33. As a variant on the free-electron model applied to benzene, assume that the six  electrons are delocalized
within a square plate of side ‘a’. Calculate the value of ‘a’ that would account for the 268 nm ultraviolet
absorption in benzene.
34. Consider a particle of mass m confined in a 3D (cubic box) of length d.
 (i) What values of nx, ny and nz correspond to the zero point energy? Write down the expression for the
zero-point energy of the system
(ii) Identify the different combinations of nx, ny and nz upto five (5) times the zero-point energy. Mention
the degeneracy of each of these energy levels.

Other integrals:

x3 1 2 1 1
 x sin xdx   x sin 2 x  x cos 2 x  sin 2 x
2 2

6 4 4 8

Feel free to use any standard integrals.