3

Particle in a box

A simple system for which the time-indenpent Schrodinger equation can be

solved exactly is the particle in a box. The particle in a box is represented
by a small region in space where inside the box the potential is zero and at
its wall and out side is infinite. Thus, the particle is free to move inside to
box since it experience no forces, but remain in the box since the walls are
infinitely high. While this is system might seem very abstract it can to some
degree be used to gain insight into the optical properties of e.g. quantum
dots and conjugated molecules.

3.1

Particle in a 1D-box

The particle in a 1D box of length L is represented by a potential given by

for x ! 0

0
for
0<x<L
V (x) =
(59)

for x " L
From this we can see that outside the box the wavefunction must be zero
since
!2 d2 I (x)
2m dx2
2 2
1 ! d I (x)
=0
I (x) =
2m dx2
I (x) =

(60)
(61)

Therefore, we only need to solve the Schrodinger equation for the particle
inside the box

!2 d2 II (x)
+ V (x) = EII (x)
2m dx2
12

(62)

!2 d2 II (x)
+ EII (x) = 0
2m dx2
d2 II (x) 2m
+ 2 EII (x) = 0
dx2
!
y !! + qy = 0

(63)
(64)
(65)

Which we recognize as a linear homogenous second-order differential equation

with constant coefficients. We know that the solution is of the form y = esx
and we can write the auxiliary equation as
s2 + 2mE!2
s2 + q
s
s

=
=
=
=

0
0

i q

s = i 2mE/!

(66)
(67)
(68)
(69)
(70)

Therefore, the solution is given by

II (x) = c1 expi

2mEx/!

+c2 expi

2mEx/!

(71)

We can now manipulate the solution in the following way

where =

II (x) = c1 exp(i) + c2 exp(i)

(72)

2mEx/!. Using that exp(i) = cos() + sin() we get

II (x) =
=
=
=
=

c1 exp(i) + c2 exp(i)
c1 cos() + ic1 sin() + c2 cos() + ic2 sin()
c1 cos() + ic1 sin() + c2 cos() ic2 sin()
(c1 + c2 ) cos() + (ic1 ic2 ) sin()
A cos() + B sin()

(73)
(74)
(75)
(76)
(77)

where A and B are two new arbitrary constants. We can determine these
constants by applying the boundary conditions. We will postulate, reasonable, that the wavefunction needs to be continuous, therefore, we require that
the wavefunction is also continuous at the boundary
lim I = lim II

x0

(78)

x0

0 = lim II {A cos() + B sin()}

(79)

0 = A cos(0) + B sin(0) = A

(80)

x0

13

Therefore,
II (x) = B sin()
Applying the boundary condition at x = L we get

II (x) = B sin( 2mEL/!) = 0

(81)

(82)

This is satisfied for

2mEL/! = n n = 1, 2, 3,

(83)

What about n = 0? This corresponds to II (x) = 0 and thus no particle.

This gives us the energy
n2 h2
n2 2 !2
=
(84)
2mL2
8mL2
Therefore, we see that quantization of the energy for the particle in a box
comes directly as a results of the Schrodinger equation. The wavefunction is
$ nx %
II (x) = B sin
, n = 1, 2, 3,
(85)
L
How do we then determine B? We use the normalization requirement
&
|(x)|2 dx = 1
(86)

& L
|(x)|2 dx = 1
(87)
0
& L
$ nx %
2
|B|
sin2
dx = 1
(88)
L
0
L
(89)
|B|2 = 1
2
'
|B| = 2/L
(90)
E=

where we have used that

&

sin2 bxdx =

1
x
sin(2bx)
2 4b

(91)

from Table A.5 on page 721 on Levine. Therefore, the final solution for the
wavefunction is
(
$ nx %
2
II (x) =
sin
n = 1, 2, 3,
(92)
L
L
14

where n is the quantum number. Draw the first few solution of the wavefunction on the board, and the square of the solutions as well. Compare this
with what is expected from classical physics ? Where is the particle ? What
happens when n goes toward ? In this limit we reach the classical results
of uniform probability density. This is known as the Bohr correspondence
principle.
We know that the wavefunction is normalized so
&
i i dx = 1
(93)

However, what is we use two wavefunctions with different quantum numbers

&
& L

i j dx = 2/L
sin(ni x/L) sin(nj x/L)dx = 0
(94)

where we have used the integral table in Appendix. There, two wavefunctions
with different quantum numbers are orthogonal
&
i j dx = ij
(95)

where ij is Kronecker delta, which is one if i = j otherwise zero.

3.2

Particle in a rectangular well

Need assistance to write down potential. Consider a particle in a 1D box

trapped in a finite potential

for x ! 0
V0
0
for 0 < x < L
V (x) =
(96)

V0
for x " L

We assume that the energy is less than V0 . The Schrodinger equation for the
article outside the box is
d2 2m
+ 2 (E V0 ) = 0
dx2
!

(97)

We recognize that this is a linear homogenous differential equation with an

auxiliary equation given by
s2 +

2m
(E V0 ) = 0
!2
15

(98)

for which the roots are

s = (

2m 1/2
) (V0 E)1/2
!2

(99)

Therefore, the solution outside the box is

2m 1/2
2m
) (V0 E)1/2 x) + D exp(( 2 )1/2 (V0 E)1/2 x) (100)
2
!
!
2m
2m 1/2
= F exp(( 2 ) (V0 E)1/2 x) + G exp(( 2 )1/2 (V0 E)1/2 x) (101)
!
!

I = C exp((
III

where C, D, F, G are constants to be determine from the boundary conditions.

Since I most be finite for x D has to be zero, similarly since III
has to be finite as x F has to be zero. Therefore, the complete solution
is
2m 1/2
) (V0 E)1/2 x)
!2
2m
2m
= A cos(( 2 )1/2 (E)1/2 x) + B sin(( 2 )1/2 (E)1/2 x)
!
!
2m 1/2
III = G exp(( 2 ) (V0 E)1/2 x)
!
I = C exp((

II

(102)
(103)
(104)

We see that outside the box, the wavefunction decays exponentially whereas
inside it is oscillatory. Therefore, the particle are allow in a region of space
which is classically forbidden. To determine the four constants left we used
that the wavefunction and its first derivative is smooth at the boundary
I (0) = II (0)
II (L) = II (L)
!
I! (0) = II
(0)
!
!
II
(L) = II
(L)

The determination of the constants are left for the home work. This gives us
the following equation for the energy
(2E V0 ) sin[(2mE)1/2 L/!] = 2(V0 E E 2 )1/2 cos[(2mE)1/2 L/!](105)
2(V0 E E 2 )1/2
tan[(2mE)1/2 L/!] =
(106)
(2E V0 )
16

which cannot be satisfied for all energies. Sketch the first solution of the
wavefunction. We have seen that for the situation of of finite potential that
there is a non-zero probability for the wavefunction to be outside the walls
even though the total energy is less than the kinetic energy. Classically this is
forbidden since the kinetic energy is always positive. This is called tunneling
and we see that the larger the mass m the faster the wavefunction decays
outside the box, thus, tunneling is more prevalent for small mass.

3.3

Particle in a 3D-box

We consider a particle in a box with lengths a, , b, and c which is centered

with one corner at the origin. The potential is then given by

0<x<a

0<y<b
V (x, y, z) =
(107)
0<z<c

elsewhere
We know that the particle outside the box must be zero. Within the box the
potential is zero and the Schrodinger equation is given as
* 2
+
!2 2
!2

2 2

(x, y, z) = E(x, y, z) (108)

(x, y, z) =
+
2m
2m x2 y 2 z 2
To solve this equation we assume that the wavefunction can be written as
(x, y, z) = f (x)g(y)h(z)

(109)

Lets differentiate this function twice with respect to x, y, z

2 (x, y, z)
= f !! (x)g(y)h(z)
x2
2 (x, y, z)
= f (x)g !! (y)h(z)
y 2
2 (x, y, z)
= f (x)g(y)h!!(z)
z 2

(110)
(111)
(112)

Substituting this back into the Schrodinger equation gives

!2
!2
!2 !!
f (x)g(y)h(z)
f (x)g !! (y)h(z)
f (x)g(y)h!!(z)Ef (x)g(y)h(z) = 0
2m
2m
2m
(113)
17

Dividing by the wavefunction we get

or

!2 f !! (x) !2 g !! (y) !2 h!! (z)

E =0
2mf (x) 2mg(y) 2mh(z)

!2 g !! (y) !2 h!! (z)

!2 f !! (x)
= Ex =
+
+E

2mf (x)
2mg(y) 2mh(z)

(114)

(115)

since the the two sides of the equations depend only different variables they
can only be true if Ex is a constant. Thus, we get with a similar argument
for y and z
!2 f !! (x)
2mf (x)
!2 g !! (y)
Ey =
2mg(y)
!2 h!! (z)
Ez =
2mh(z)

Ex =

(116)
(117)
(118)

The total energy is then given by

E = Ex + Ey + Ez

(119)

We have managed to use separation of variable to transform the 3D partial

differential equation into 3 1D differential equations given by
d2 f (x) 2m
+ 2 Ex f (x) = 0
dx2
!
d2 g(y) 2m
+ 2 Ey g(y) = 0
dy 2
!
2
d h(z) 2m
+ 2 Ez h(z) = 0
dz 2
!

(120)
(121)
(122)

We know the solution to these equation of the 1D box, and the wavefunction
in the x direction is
* +1/2
$ n x %
2
x
sin
(123)
f (x) =
a
a

and the energy

Ex =

n2x h2
, nx = 1, 2, 3,
8ma2
18

(124)

Similar the solutions in the y direction is

* +1/2
+
*
2
ny y
g(y) =
sin
b
y
2 2
ny h
, ny = 1, 2, 3,
Ey =
8mb2

(125)
(126)

and z direction
* +1/2
$ n z %
2
z
h(z) =
sin
c
c
2 2
nh
Ez = z 2 , nz = 1, 2, 3,
8mz

(127)
(128)

Thus the solution to the Schrodinger equation for the particle in a 3D box is
by a energy
+
*
h2 n2x n2y
(129)
+ 2 n2
E=
8m a2
b c2z
and a wavefunction
*
+1/2
$ n y %
$ n z %
$ n x %
8
x
y
z
(x, y, z) =
sin
sin
sin
abc
a
b
c
We also know that the wavefunction is normalized
&
& & &
2
|(x, y, z)| d =
|(x, y, z)|2dxdydz

& a
0

|f (x)| dx

&

|g(y)| dy

&

(130)

(131)

|h(z)|2 dz = 1(132)

Now lets consider a cube, i.e. a = b = c. The energy of a particle in cubic

box becomes
*
+
h2
h2 n2x n2y n2z
+
+
=
(n2x + n2y + n2z )
(133)
E=
2
2
2
2
8m a
a
a
8ma
Ask for a volunteer to calculate the energy of quantum state (211), (121), (112).
This shows that the energy is the same for these three states due to symmetry, we call this that the energy is degenerate. The degree of degeneracy is
the number of states with the same energy.
19

3.3.1

Separations of variables

Consider the time-independent Schrodinger equation

= E
H

(134)

as
Suppose that we can write the H

+ H

H(,
) = H

(135)

Then we can write the wavefunction as a product of two functions

= f ()g()

(136)

and the solution is given in terms of two independent Schrodinger equations

f () = E f ()
H
g() = E g()
H

(137)
(138)

and thus the energy is given by a sum

E = E + E

20

(139)