Section B: Tutorial 2: Solutions

4th March 2014

1. We will check below whether the given functions are eigenfunctions of the operator

(a)

p̂2x (A sin(kx)+B cos(kx)) = −h̄2 (−k 2 A sin(kx)−k 2 B cos(kx)) = h̄2 k 2 (A sin(kx)+B cos(kx))

Eigenfunction with eigenvalue h̄2 k 2 .

(b)
x̂ekx = xekx
Not an eigenfunction
(c)
p̂x (Aekx + Be−kx ) = −ih̄k(Aekx − Be−kx )
Not an eigenfunction
(d)
2 2 2 2
(p̂2x + x̂2 )e−ax = 2ah̄2 (1−2ax2 )e−ax +x2 e−ax = (2ah̄2 +x2 (−4a2 h̄2 +1))e−ax

In order for this to be an eigenfunction, we must have the coefficient of x2

2
in the polynomial multiplying e−ax go to zero. This can only happen if
−4a2 h̄2 + 1 = 0 or a = ±1/2h̄.

2. First we normalize the function

ZL ZL !
2 2 2 1 − cos(2nπx/L)
N sin (nπx/L)dx = N dx
2
0 0

For integer n, we can showqthat the integral on the right has value L/2. Thus we
have N 2 L/2 = 1 or N = 2/L. Thus the normalized wavefunction is given by
q
2/L sin(nπx/L). Now we can calculate expectation values.

ZL
s  s
2 nπx 2 nπx
  
hxi = sin x sin dx
L L L L
0
1
 L
2Z nπx
 
= x sin2 dx
L L
0
ZL
1 nπx
  
= x 1 − cos dx
L L
0
1 L2
" # !
x sin(nπx/L) cos(nπx/L) L
= − + |0
L 2 nπ/L (nπ/L)2
= L/2

ZL
s !s
2 nπx ∂ 2 nπx
   
hpx i = sin −ih̄ sin dx
L L ∂x L L
0
L
−2inπh̄ Z nπx nπx
   
= 2
sin cos dx
L L L
0
L
−inπh̄ nπx
Z  
= sin 2 dx
L2 L
0
= 0

3. To find the wavefunction, we start with a trial wavefunction and apply the bound-
ary conditions. The trial wavefunction is taken as ψ(x) = A sin(kx) + B cos(kx).
Applying boundary conditions at x = ±L/2 we get

A sin(kL/2) + B cos(kL/2) = 0 at x = L/2

−A sin(kL/2) + B cos(kL/2) = 0 at x = −L/2

Thus, there are two possibilities:

A = 0 and cos(kL/2) = 0 i.e.kL/2 = (2n + 1)π/2

where n = 0, 1, 2, ... or

B = 0 and sin(kL/2) = 0 i.e.kL/2 = nπ

where n = 1, 2, .... The energy of the state is given by

h̄2 k 2
Ek =
2m
where k = n0 π/L where n0 = 1, 2, 3, .... The wavefunction is given by

ψn0 (x) = A cos(n0 πx/L) for n0 odd

ψn0 (x) = B sin(n0 πx/L) for n0 even

 Normalization
q of the wavefunction is just like the particle in a box and will lead
to A = B = 2/L. The ground state is given by
s
2 πx
 
ψ1 (x) = cos
L L
The first and second excited states are given below
s
2 2πx
 
ψ2 (x) = sin
L L
s
2 3πx
 
ψ3 (x) = cos
L L
Thus the wavefunction of the 2nd excited state is given by ψ3 (x) above. To
calculate the expectation value of x̂2 in the above state, we write
L/2
2 2 3πx
Z  
2
hx i = x cos2 dx
L L
−L/2

The integral on the right hand side has to be evaluated by parts twice. It is a
fairly long procedure that we outline below.
L/2
1 2 6πx
Z   
2
hx i = x 1 + cos dx
L L
−L/2
L/2 L/2
x2 1 2 6πx
Z Z  
= dx + x cos dx
L L L
−L/2 −L/2
L/2
L2 1 6πx 1 Z 6πx
    
L/2
= + x2 sin |−L/2 − x sin dx
12 6π L 3π L
−L/2
L/2
L2 L 6πx L Z 6πx
    
L/2
= − 2
−x cos |−L/2 − cos dx
12 18π L 18π 2 L
−L/2
2 2
L L
= −
12 18π 2
Check that the final answer also has the correct dimensions.

4. For 1,3,5-hexatriene, we assume that the 6 pi electrons are delocalized over the
length of the molecule and do not interact with each other. The length of the box
is approximately five times the length of the C-C bond. However, we assume that
the delocalization goes out of the terminal carbon atoms to a distance of half the
bond length on either side. Thus the length of the box is taken as 5+0.5+0.5 =
6 times the length of the C-C bond. Further, we treat the electrons as fermions
and not more than two electrons can be in a single energy level. So, the first three
energy levels are filled and the fourth level is empty in the ground state. Thus,
the longest wavelength (least energy) of light absorbed corresponds to a transition
of an electron from level 3 to level 4.
hc 7h2
= E4 − E3 =
λ 8mL2
Using L = 6l where l is the length of the C-C bond, we can write

288ml2 c 288 × 9.1 × 10−31 kg × (1.3 × 10−10 m)2 × 3.0 × 108 m/s
λ= =
7h 7 × 6.626 × 10−34 Js

= 286 × 10−9 m = 286nm