CHEM106: Assignment 5

Particle in a Box

1. For a one-dimensional particle in a box system, the solution of the Schrdinger

n 2h 2
En
equation leads to the quantized energy 8mL2 . What is the zero-point energy for
the system?

The zero-point energy (ZPE) for a quantum mechanical system is defined as the
lowest possible energy allowed. In the case of the harmonic oscillator, the energy
depends on the quantum number n, and n = 1, 2, 3, .
12 h 2 h2
ZPE E1
Thus, 8mL2 8mL2 .

2. The -electron of a conjugated polyene molecule can be modeled as a particle in a

box. Assuming a length of 0.6 nm for the one-dimensional box,

A. calculate the energy gap between the first excited state and the ground state for
the electron.

For the one-dimensional particle in a box, the energy is given by

n 2h 2
En
8mL2 .
The energy gap between the first excited state (n = 2) and the ground state
(n = 1) is
E E2 E1
2 2 h2 12 h2

8meL2 8meL2
3h2

8meL2
3 (6.626 10 34 J s)2

8 9.1093897 10 31 kg (6 10 10 m)2
5.02 10 19 J .

B. what is the corresponding frequency of the photon absorbed as the electron

makes a transition from the ground state to the first excited state?

E h
E / h 5.02 10 19 J / 6.626 10 34 Js 7.58 1014 Hz
3. For a one-dimensional particle in a box system, the solution of the Schrdinger
2 n
n ( x ) sin( x)
equation generates a wave function L L for the state n. Verify that
n (x ) satisfies the Schrdinger equation.

For the one-dimensional particle in a box system, the Hamiltonian operator can be
defined as
2 d 2 2 d 2
H T V 0
2m dx 2 2m dx 2 .
When we operate the Hamiltonian on the wave function, we obtain
(x) d
2 2
2 n
H n 2
sin( x)
2mdx L L
2 n 2 2 n
( ) sin( x)
2m L L L
n2 h2 2 n
2
sin( x)
8mL L L
En n(x).
Thus, the given wave function n (x ) satisfies the Schrdinger equation.

2 x
1 ( x ) sin
4. For the ground state of the particle in a box system L L , calculate the
probability of finding the particle between x = 0 and x = L/2.

1 1
sin (x )d x x sin( 2x )
2

2 4
[Useful integral: ]

The probability of finding the particle between x = 0 and x = L/2 is

L/l L/2 L/2
2
p * ( x ) ( x )d x sin( x ) sin( x )d x sin 2 ( x )d x
L 0 L L L
0 0 .
1 1
sin (x )d x 2 x 4 sin( 2x )
2

According to the given above, ,

we have
2 1 L 2 L/2
P [ x sin( x)] 0
L 2 4 L
2 L L 2 L
{ [sin( ) sin(0)]}
L 4 4 L 2
2L 1
.
L4 2
5. Find out the degeneracies of the lowest four energy levels for the three- dimensional
particle in a box system with the dimension L x = Ly = Lz.

The energy for the three-dimensional particle in a box system is given by

n x2 h 2 n 2y h 2 n z2 h 2
E Ex E y Ez
8mL2x 8mL2y 8mL2z
.
If Lx = Ly = Lz, the above expression reduces to
h2
E ( n x2 n 2y n z2 )
2
8mLx .
The degeneracy of an energy level equals to the number of quantum states for the
given energy. The lowest four energy levels and the corresponding degeneracy is
listed below:

Energy Levels
h2 Possible States
Degeneracy
2 nx ny nz
(in units of 8mL )x

3 111 1
6 1 2 1, 2 1 1, 1 1 2 3
9 2 1 2, 2 2 1, 1 2 2 3
12 222 1