Quantum Chemistry II, Homework I

by Albeiro Restrepo
May 31, 2009

1 Problem
Discuss how the postulates of Quantum Mechanics help explain sequential
Stern-Gerlach experiments.

2 Problem
Discuss the role of commutators in measurements and in the uncertainty
principle.

3 Problem
Let |ψ1 i and |ψ2 i be two orthogonal normalized states of a physical system:

hψ1 |ψ2 i = 0 and hψ1 | ψ1 i = hψ2 |ψ2 i = 1

and let A be an observable of the system. Consider a non degenerate eigen-

value of A denoted by αn to which the normalized state |φn i corresponds.
We define P1 (αn ) = |hφn | ψ1 i |2 and P2 (αn ) = |hφn | ψ2 i |2 . (a) What is the
interpretation of P1 (αn ) and P2 (αn )? (b) A given particle is in the state
3 |ψ1 i − 4i| ψ2 i. What is the probability of getting αn when A is measured?

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4 Problem
Consider a chemical system with a three–dimensional state space. An or-
thonormal basis of the state space is chosen; in this basis the Hamiltonian is
represented by the matrix
 
2 1 0
 
H= 1 2 0 
0 0 3
(a) What are the possible results when the energy of the system is measured?
(b) Suppose that the energy of the system was measured and a value of ε
= 1 was found. Subsequently, a measurement of a property represented by
operator A is performed. The matrix representation for A in the same basis
is
 
5 0 0
 
A= 0 2 i 
0 −i 2
Find the possible results for the measurement of A. (c) Find the probabilities
of obtaining each of the results in (b). (d) Suppose that after measuring H
and A, we measure H again. What energy is obtained? (e) Does the value of
H in (d) depend on the previous measurements? (f) Does the conservation
of energy principle hold?

5 Problem
One thousand electrons are in a one–dimensional box (a string of metal
atoms, for example) with walls at x = 0 and x = a. At a given time,
the state of each particle is ψ(x) = Ax(x − a). (a) Normalize ψ and find the
value for the constant A. (b) How many particles are in the interval (0, a/2)?
(c) How many particles have energy ε5 ? (d) What is hεi?

6 Problem
A one–dimensional box containing an electron suffers an infinitesimal per-
turbation and emits a photon of frequency hν = 3ε1 . Where ε1 denotes the
ground state of the particle. A student concludes that the electron was in
the state φ2 prior to the perturbation. What is your opinion?

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7 Problem
Prove the following identities for operators A, B and C: (a) [B, A] = −[A, B].
(b) [A + B, C] = [A, C] + [B, C]. (c) [A, BC] = [A, B]C + B[A, C].

8 Problem
For square matrices prove: (a) tr AB = tr BA. (b) (AB)−1 = B−1 A−1 . (c)
If U is unitary and B = U† AU, then A = UBU† . (d) If the product C =
AB of two Hermitean matrices is also Hermitean, then A and B commute.

9 Problem
(a) Show that the trace of a matrix is invariant under unitary transforma-
tions. (b) Show that the length of vectors is invariant under rotations. Hint:
Remember that rotations can be achieved by multiplying teh coodinate vec-
tors a a unitary matrix.

10 Problem
Consider the sets of vectors {~ ~ and {~v , w}
α, β} ~ defined as follows
√ √ √ √
2 2 2 2
α
~= (1, 1), β~ = (−1, 1), ~v = (−1, −1), w~= (1, −1)
2 2 2 2
(a) Write all the vectors in vector and Dirac notations (all bras and kets).
(b) Find the matrix representation for all the bras and kets. (c) Find all the
possible dot products. (d) Prove that {~ ~ and {~v , w}
α, β} ~ are basis for R2 . (e)
Write the vectors {~ ~ in terms of the vectors {~v , w}
α, β} ~ and viceversa. (f)
Find the transformation matrix for going from one basis to the other and its
adjoint. (g) Evaluate Uα, Uβ, U† v, U† w. (h) Prove that U is unitary. (i)
Find the angles between each pair of vectors.

11 Problem
Prove that the matrix representations of an operator on two different basis
are related via a unitary transformation.

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12 Problem
(a) Prove that the eigenvalues of Hermitean operators are real. (b) Prove
that the eigenfunctions of a Hermitean operator are orthonormal. (c) What
is the matrix representation of a Hermitean operator on the basis of its
eigenfunctions?