Lecture 3

Particle in a Box
In the coming few chapters, we will solve Schrdinger equation (SE) for various simple
model systems (with increasing complexity).
The recipe for solving SE is as follows:
Define the potential energy function (system dependent)
Define the boundary conditions (system dependent)
Write down the Hamiltonian operator for the system and solve the resulting SE
to obtain a general solution for the differential equation.
Find particular solution applying the boundary conditions
In the current chapter, we solve the quantum mechanical problem of a particle entrapped in an infinite potential well (box). This chapter helps to learn how to solve SE
and analyze the solutions.

3.1

Solving Schrdinger Equation for Particle in a One

Dimensional Box

Suppose we have a particle of mass m confined in a onedimensional box of length

L (for e.g. a particle moving in a piece of a straight wire). Let us consider that the
potential inside the box is zero. The ends of the box are at x = 0 and x = L and the
potential at these positions are infinite such that the particle cannot escape the box.
1

V =1

V =1

V =0
x=L

x=0

For the particle within the box, we can write the Hamiltonian operator:
h 2 d2
+ V (x)
H =
2m dx2
h 2 d2
=
+0
2m dx2
h 2 d2
=
2m dx2

(3.1)

We are not interested in Hamiltonian operator of the particle outside the box, as particle
will have zero probability to be outside the box (and thus wavefunction = 0) which is
forced by the infinite potential at x = 0 and x = L.
Now, the Schrdinger equation for the particle is
( x ) = E( x )
H
h 2 d2

= E( x )
2m dx2
d2
2mE
=

( x )
dx2
h 2

(3.2)

We are interested to solve the above equation, and thus to obtain , for certain values
of E. But how to get E?
From the above equation, it is clear that ( x ) is such that when it is differentiated
twice with respect to x, the original function is recovered but multiplied by a constant
(2mE/h2 ). Thus, we can try a trignometric or an exponential function as the trial
solution. Let,
( x ) = A sin kx + B cos kx
where A, B and k are constants. The above is a general solution for the second order
differential equation in Eqn. 3.2.
2

Applying boundary conditions, (0) = 0 and ( L) = 0. This implies that cosine

terms cannot be present in the particular solution. Thus we conclude that
B=0
Also, we infer
kL = n, n = 1, 2 .
Thus,
n ( x ) = A sin

 n 
x , n = 1, 2,
L

(3.3)

Notice that, has the subscript n, as it depends on the integer number n. Substituting,
Eq. 3.3 in Eq. 3.2, we get,

 n 2
L

( x ) =

2mE

( x )
h 2
n2 2 h 2
E =
2mL2
n2 h2
, n = 1, 2,
=
8mL2

(3.4)
(3.5)
(3.6)

The above shows that energy (i.e. the kinetic energy of the particle) depends on the
integer n. Thus we introduce a subscript for E, and thus
En

n2 h2
=
, n = 1, 2,
8mL2

(3.7)

In other words, energy is quantized by the presence of n, and n is called as a quantum

number. For any n, there is a certain energy En and a wave function n given by
Eqn. 3.3. Notice that quantum numbers arise due to the boundary conditions that
leaves the quantum mechanical particle in a bound state, thus resulting in standing
waves; see Eqn. 3.3. State of the quantum mechanical system is characterized by the
wave function n ( x ) with quantum number n. The ground state is the state which
has the lowest energy, i.e. n = 1 and is characterized by the wave function 1 ( x ) ; all
the other states are excited states. The first excited state is having n = 2.
(Think: What about electrons in an atom? Do you expect quantization of energy? )
Note that n = 0 is not considered here because it will result in 0 ( x ) = 0 for all the
values of x. This is not a physically correct result as it will lead to zero probability of
finding the particle within the box.
3

It is also worth noting that the energy of the lowest energy level, i.e. the zero-point
energy, is equal to h2 /(8mL2 ). If zeropoint energy was zero, implying that kinetic energy of the particle will be zero in the ground state, its velocity is zero always. Following
the Heisenberg uncertainty principle, if velocity is zero, the uncertainty in determining
its position x would become infinity. However, since the boundary potentials are infinite, the uncertainty in determining the particles position cannot exceed L. Thus, zero
value for zeropoint energy is not acceptable.
We have seen that
E

1
.
m

Thus for large mass, energy difference between successive energy levels would be very
small. Thus, energy of such system may be considered not quantized, rather vary
continuously like for a classical case. Also,
E

1
.
L2

Thus, if the container has macroscopic dimension, then the energy varies very small,
and may be also considered as varying continuously. These show that, quantum mechanical effects disappear for macroscopic systems, and they behave classical.

3.2

Wavefunction
Z L
0

dx ( x )( x ) = 1

Z L

 nx 
dx B2 sin2
=1
L
0



Z L
1
2nx
2
B
=1
dx 1 cos
2
L
0
L
B2 = 1
2r
2
B=
L
Thus,

r
n ( x ) =

 nx 
2
sin
, n = 1, 2
L
L

n (x)

E4

E3

|
+

n (x)|

E2

+
+

E1

Figure 3.1: n ( x ) and |n ( x )|2 for the energy levels with n = 1, 2, 3, and 4 for a particle in
a box.

Nodes are the points, except the boundaries, where ( x ) = 0. Number of nodes
increases with n for a particle in a box wave function. It may be also noted that the
distance between maxima decreases with n, thus a nearly uniform probability density
is achieved when n .

3.3

Computing Properties of Particle in 1-D box

Probability distribution, given by

( x )( x )
can be used to compute averages and standard deviation.
Average position of a particle in a box with walls at x = 0 and x = L is given by

hxi =

dx ( x ) x( x )

(3.8)

2 L
nx
=
dx x sin2
L 0
L
2
L
2L
=
(for any value of n)
=
L 4
2
Z

(3.9)
(3.10)

Note: above we use the identity

1
(1 cos 2x )
2

sin2 x =
and integral by parts
Z

where G ( x ) =

dx f ( x ) g( x ) = f ( x ) G ( x )

dx

df
G(x)
dx

dx g( x ).

Similarly, one may compute

D E
x2
=

2 L
nx
dx x2 sin2
L 0
L
2
2
L
L
=
2 2
3
2n
Z

Average momentum can be computed as

"
#
#
 "r
Z L r
2
nx
d
2
nx
<p> =
sin
ih
sin
L
L
dx
L
L
0
2
n
(ih)
L
L
= 0

Z L
0

sin

nx
nx
cos
L
L

(3.11)
(3.12)

(3.13)
(3.14)
(3.15)

Note: we use the identity here

sin 2x = 2 sin x cos x
Similarly, you can show that
"r
Z

< p2 > =
=

2
nx
sin
L
L

#

d2
h 2 2
dx

 "r

2
nx
sin
L
L

n2 2 h 2
L2

(3.16)
(3.17)

Variance, 2 , is a measure of the spread of a spread of a distribution about its mean

value. Thus we can interpret that 2 measures the uncertainty. We know that,
D E
x2 = x2 h x i2
and
p2

2 n2
2
3

= p

h p i2

then,
h
x p =
2

1/2

which is in consistent with the Heisenberg uncertainty principle,

x p >

3.4

h
2

Origin of Quantization

We realized while solving particle in a box problem that we solve the wave functions
only for some values of E. In general, it is impossible to find an quantum mechanically
acceptable solution to the problem for an arbitrary value of E. Note that for any arbitrary
value of E we can have a mathematically acceptable solution, but this might not give
us a well behaving solution, which is required by quantum mechanics.
The quantized energy levels or quantum numbers is a consequence of the boundary
conditions. Quantization will occur only when the particle is confined to a finite region
of space by the potential.
In Figure 3.2 for energy E > E0 , particle is not confined, and behave like a free
particle (see also the Practice Problem Set 2, Question No. 9).
7

E1

E
Non quantized
states

E0

Non quantized states

E0

V (x)

V (x)

quantized
states

quantized
states

Figure 3.2: Quantized and non quantized energies arising due to the boundary conditions

3.5

Quantum Mechanical Tunneling

When the potential wall encompassing the particle is not infinitely high, then particle
would escape, even when its kinetic energy is not as large as the potential barrier. There
is a finite probability of finding the particle outside the box, even if the kinetic energy of
the particle is smaller than the barrier, which is called a quantum-mechanical tunneling.
This phenomenon is having large importance in chemistry and biology. Reaction rate is
controlled by the number of reactant molecules acquiring sufficient energy to overcome
the activation energy barrier. But, if tunneling occurs, reaction can take place even
when molecules dont have sufficient energy to cross the activation energy barrier.
The technique called the scanning tunneling microscope (STM), which is used for
imaging surface at an atomic level resolution, is based on the principle of quantum
tunneling. A voltage is applied between an electrode tip and a metallic surface. The
electrons are allowed to tunnel from the tip to the surface. Tunneling current depends
on the distance of the tip from the surface, and thus helps to image the surface structure
of the metallic surface.

V (x)
(x)
Vb

Vb

Vb
x
| (x)|

(b)

V (x)
Vb

(a)

(c)

Figure 3.3: Schematic diagrams showing wave function is tunneling through a finite potential
barrier for states whose energy is less than the potential barrier Vb .

Tip
e- tunneling

+
voltage

metallic surface

STM Image

Figure 3.4: Schematic diagram of STM. A sample of STM image is also shown (taken from
http://www.nanotech-now.com/news_images/33492.jpg)