CML100: Quantum Chemistry - Exercise Sheet 1

8h 3 d
1. Equation ( , T )d expresses Plancks radiation law in terms of frequency. Express it in
c 3 hkT
e 1
terms of wavelength.

2. Integrate Plancks distribution law over all frequencies to obtain the total energy emitted. What is its

x3 4
temperature dependence? What is this law known as? You will need to use the integral x .
0
e 1 15

dx 4
3. Derive Stefan-Boltzmann law starting from Plancks radiation law (hint: 1x

15
).
x e 1
0 5

4. Derive Wiens law from Plancks radiation law.
N ( )d
8h 3 d
5. We have seen that ( )d , where <> is the average energy of the
V c 3 hkT
e 1
oscillators which are assumed to make up the walls of the cavity and which are in equilibrium with the
radiation field inside the cavity, and N()d is the number of the modes of the radiation field in a cavity of
volume V in the frequency range to +d.
(a) According to classical statistical mechanics, the average energy <> for systems in thermal

equilibrium is
e kT
dpdx
. For a simple harmonic oscillator = p2/2m + 1/2kx2. Evaluate <>.


e kT
dpdx
(b) If the energy of the oscillator can only take on the values i = ih, where i is an integer, then the
i

e i
kT

integral in part (a) must be replaced by i 0
i
. Evaluate <> (hint: (1 y ) 1 y i ).

e kT i 0

i 0
6. In the Davisson-Germer experiments, a single crystal of nickel was subjected to electron diffraction. The
electron beam was accelerated through a potential difference of V volts to give it appropriate momentum. If
the spacing between the lattice planes of the nickel is 1.7 angstrom, then calculate the minimum value of V
needed to produce the appropriate de Broglie wavelength for the electrons.

7. When lithium is irradiated with light, one finds a stopping potential of 1.83 V for = 3000 and 0.80 V for
= 4000. From the data, calculate (a) Plancks constant, (b) threshold frequency, and (c) work function of Li.

8. Given = d/dx and = x2, show (a) 2f(x) [f(x)]2 and (b) f(x) f(x) for arbitrary f(x).

9. 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) eax2. Give the corresponding eigenvalue where appropriate.

10. Find the eigenvalue in the following cases:

(operator) f(x) Eigenvalue
d2 2 cos x
dx
 d exp(it)
dt
d2 d
2
2 3 exp(x)
dx dx
x 2 exp(6 y)
y

11. Write out the operator for 2 for =

d2 d d2 d
(a) 2
(b) x (c) 2
2x 1 .
dx dx dx dx
12. Find the eigenfunctions and eigenvalues of the operator d .
dx

13. In algebra it can be easily shown that (P + Q)(P Q) = P2 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 P2 Q2?

14. (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.

15. Evaluate the commutator A , B , where A and B are given below:
A B
_____________________________________
d d
(a) x x
dx dx
d2 d
(b) 2
x x2
dx dx

16. Normalize the following wavefunctions to unity: ( x n e ax dx n!/ a n1 )
0
(a) sin(nx/L) for the range 0 x L.
(b) c, a constant in the range L x L.
(c) exp(r/ao) in 3-D.
(d) xexp(r/2ao) in 3-D.
(e) (2-r/ao)exp(r/2ao) in 3-D.
(f) rsincosexp(r/2ao) in 3D

17. 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 (x,y: 0, )
2
1 1 3i 2
18. 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 E1, 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.