CH4102-Assignment I (2016) (Avoid round-about answers).

1. Porphyrin molecule is planar. Approximate the 26 electrons as being confined inside

a square. What are the energy levels and degeneracies of a particle in a square of
side a? If we approximate the length of the molecule by 1000 pm, then what is the
predicted lowest energy absorption of this molecule? (The experimental value is
17000 cm1 ).
2. Set up the problem of a particle in a box with its walls located at +a and a. Show
that the allowed energies are equal to those of a box with walls located at 0 and 2a.
Show however, that wave functions are not the same, and in this case, are given by:
1
nx
,
n (x) = sin
a
2a
1
nx
= cos
a
2a

n even
n odd

Does it bother you that the wave functions seem to depend upon whether the walls are
located at a or 0 and 2a? Surely the particle knows that it has a region of length
2a in which to move and can not be affected by where we place the origin. What
does it tell you? Will the experimentally observable quantities depend upon this fact?
Show that x p > h2 .
3. Consider a particle moving in the following potential energy (with E > V0 ): V (x) = 0
and V0 when x < 0 and x > 0 respectively. Divide the region in to separate zones. Define wave numbers k =

2mE
,
h2

k =

2m(EV0 )
.
h2

Write down the boundary conditions

and derive expressions for wave functions for x < 0 and x > 0 in terms of coefficients
A, B, C. Now find out expressions for reflection and transmission coefficients R, T .
Prove that R + T = 1. Would you have expected the particle to have been reflected?
Show that R 0 and T 1 as V0 0.
4. Consider the same problem as above with E < V0 . Proceed along the lines with

(x) = Aeikx + Beikx for x < 0, while (x) = Cek x + Dek x , for x > 0. Divide
the space into separate regions. Define wave numbers k =

2mE
,
h2

k =

2m(V0 E)
.
h2

On physical grounds (in order to prevent blow-off), let us set C = 0. Now prove that

coefficients A, B can be written as: A = (1+ ikk ) D2 , B = (1 ikk ) D2 , and

h q

B
A

= ei , where

= 2 tan1 ( VE0 1) . Also show that, (x) = 2Aei/2 cos(kx 2 ), for x < 0,
1

and (x) = 2Aei/2 cos( 2 )ek x , for x > 0. Prove that, there is complete reflection,

i.e., R = 1, in this case, in accordance with classical mechanics. However show that,
there is a finite probability of finding the particle in x > 0 region. This non-classical
phenomenon is called barrier penetration.