CH 231–Introduction to Quantum Chemistry

a a  Z a
a2 a3
Z Z  2 2
nπx nπx 4π n nπx mπx a
x sin2 dx = , x2 sin2 dx = 2 2
− 2 , sin sin dx = δnm ,
0 a 4 0 Z a 8π  n 3 0
 a a 2
2 nπ x x a 2nπ x
sin dx = − sin
a 2 4nπ a

   
1 0 1
1. Two basis kets are defined as |+i= and |−i= . Consider two state vectors, |1i = √ [|−i − i|+i] and
0 1 2
1
|2i = √ [|+i − i|+i].
2
(a) Represent the state kets in column vector format with respect to the set of basis sets {|+i, |−i}. Calculate
h1|1i and h2|1i.

(b) Consider the operation Â|±i = ± 21 i~|∓i and that the matrix form of the operator  is
 
h+|Â|+i h+|Â|−i
 = .
h−|Â|+i h−|Â|−i

Find Â|1i and show that |1i is an eigenstate of Â. What is the eigenvalue.

2. A quantum state of a particle-in-a-box system is described by Ψ = (cos α) eikx + (sin α) e−ikx , where α is a
parameter. What is the probability that the particle will be found with a linear momentum i. k~, ii.−k~? What
form would the wavefunction have if it were 60 percent certain that the particle had a linear momentum +k~?
(5)
1
3. The flux density in the x-direction is defined as (Ψ∗ px Ψ + Ψ p∗x Ψ∗ ). Use Ψ = A eikx and show that the
2m
flux density is the velocity of the particle multiplied by the probability that the particle is in that particular
state.

4. Suppose that Ψ1 (x) and Ψ2 (x) are both solutions to the time-independent Schrödinger equation for the same
potential energy U (x). Prove that the superposition Ψ(x) = Ψ1 (x) + Ψ2 (x) is also a solution to the time-
independent Schrödinger equation.

5. Prove that the kinetic energy operator is hermition.

6. Is x̂ + ip̂ hermitian? Use bracket notations to show.

7. Let  be a linear operator and |ai be a set of basis vectors. The trace of the operator is defined as T r(Â) =
P
a ha|A|ai.

(a) Show that T race is independent of basis and T r(|φihψ Â) = hψ|Â|φi
h i
8. A linear operator is said to be normal if it commutes with its adjoint, Â, † =0. Let | ai be an eigenvector,
 | ai = a | ai.

(a) Show that Hermitian and unitary operators are normal.

 (b) Show that † | ai = a∗ | ai marks)

9. Show that ↠is hermitian conjugate of â, i.e. hψ1 | â | ψ2 i = hψ2 | aˆ† | ψ1 i∗
p
10. The ground-state wavefunction for a particle confined to a one-dimensional box of length a is ψ = 2/a sin( πax ).
Suppose the box is 10.0 nm long. Calculate the probability that the particle is (a) between x = 4.95 nm and
5.05 nm, (b) between x = 1.95 nm and 2.05 nm, (c) between x = 9.90 nm and 10.00 nm, (d) in the right half
of the box, (e) in the central third of the box

11. The wavefunction inside a long barrier of height V is ψ = N e−kx . Calculate i. the probability that the particle
is inside the barrier and ii. the average penetration depth (i.e., hx̂i) of the particle into the barrier.

12. Assuming that operators

 themselves
 are time-independent, derive the time-dependence of the expectation value
dhAi
of an operator  i.e., in terms of its commutator with the Hamiltonian. From this, derive the Ehrenfest
dt
theorem which expresses the time-dependence of the expectation values of the position and the momentum
operators of a particle in one-dimension. Look at the Ehrenfest theorem from the prescribed book or a good
website.

13. For a particle of mass m moving in one-dimensional box of length a, with ends of the box located at x = 0 and x
dx
= a, the classical probability density can be shown to be independent of x and given by P (x)dx = regardless
a
of the energy of the particle. Evaluate the probability that the particle is within 0 and a/4. Evaluate the
corresponding probability for a quantum particle between 0 and a/4. Show that as n approaches ∞, quantum
results approach classical results.

14. Suppose that a particle is in the state

r
30
Ψ(x) = x(a − x), for 0 ≤ x ≤ a
a5
= 0, otherwise.

See that Ψ(x) is not an eigenfunction for particle in a box. Normalize Ψ. What is the average energy associated
with this Ψ.

15. In the above question, Ψ is not an eigenfunction. As we have said in the class, any unknown function can be
written as a linear combination of r eigenfunctions. In this case, let us write the above Ψ as a linear combination
2 nπx
of particle in a box functions, i.e., sin . Find out the expansion coefficients. You will be having separate
a a
coefficients for odd and even states.

16. In the class, we have discussed the case of a particle in a one-dimensional box for which the the wavefunction
is of the form Ψ = A cos κx + B sin κx. This system is similar to a ”stick with negligible width along which
the particle moves”. Let us consider the benzene molecule. Although it is hexagonal, to a crude approximation,
we can think of benzene as a stick in which the two ends are joined in such a way that it is difficult to locate
the position of UNION. In addition, it is difficult to identify the seam. Solve the TISE for this system with
 appropriate boundary conditions. What will be the ground state quantum number? Write the expresssion for
energy in terms of quantum number. How does the ground state look like?
X
17. Consider the quantum state Ψ = cn φn e−iEn t/~ , where φn s are the eigenfunctions of the Hamiltonian oper-
n
ator. SHow that hEi is time-independent, where E stands for energy? Under what condition, hAi (where A is
an operator other than the energy operator) will also be time-independent?

18. Consider that a particle is confined to move inside a box whose boundaries are at -a and +a. This shows that
the length of the box is doubled to 2a, compared to the box with boundaries at 0 and a. Will this have an effect
on the format of eigenfunctions? Solve the TISE. How the eigeneneries would look like?

19. What are the most likely locations of a particle in a box of length L in the state n = 3 (boundaries are at 0 and
a)?

20. To a crude first approximation, a π electron in a linear polyene may be considered to be a particle in a one
dimensional box. The polyene - carotene contains 22 conjugated C atoms, and the average internuclear distance
is 140 pm. Each state up to n = 11 is occupied by two electrons. Calculate (a) the separation in energy between
the ground state and the first excited state in which one electron occupies the state with n=12. (b) The
frequency of the radiation required to produce a transition between these two states (c) The total probability
of finding an electron between C atoms 11 and 12 in the groundsate of the 22-electron molecule.

21. Set up the Schrödinger equation for a particle of mass m in a two-dimensional infinite well with sides Lx and Ly ,
along x and y, respectively. Use separation of variables procedure (to separate x and y) to solve the TISE and
show that the wavefunction is defined by two quantum numbers. Find the energy levels. Is there a possibility
that two states could be degenerate in this case?

22. When a hydrogen atom undergoes a transition from n=2 to n=1 level, a photon with λ=122nm is emitted. (a)
If the atom is modeled as an electron trapped in a one-dimensional box, what is the width of the rigid box in
order for the n=2 to n=1 transition to correspond to emission of a photon of this energy? (b) For a box with
the width calculated in (a) , what is the ground state energy? (c) by how many eV is this energy different from
the ground state energy of the Hydrogen atom?