Chemistry 101

Particle-in-a-Box (PIB)...
The 2nd and 3rd Dimensions...
Introduction - Results from 1-D
In lecture,
the Schrodinger equation for the wave function
qwe solved
 nx
n2 h2
2
n (x) = L sin L and for the energy En = 8mL
2 for a bead-on-a-string, i.e.,
for a particle in a 1-D box. In the expressions for n (x) and for En , n is the
quantization parameter, i.e., the quantum number n = 1, 2, 3, ... We will see that
the 3-D box wave function is simply a multiplication of three 1-D wave functions
such that each wave function piece has a unique quantum number - denoted
nx , ny , or nz accordingly - and a unique length - similarly denoted Lx , Ly , or Lz
accordingly. The energy also will have three contributions - each contribution of
the same mathematical form as the 1-D energy formula - except that each
contribution will have its unique n (nx , ny , nz ) and L (Lx , Ly , Lz ). First we will set
up the results for the 3-D case and then merely list the results for the 2-D case,
hoping that you will agree with the results. Here goes.
Extending the 1-D Results to a 3-D box and to a 2-D corral
If one were to work out the details for the PIB in 3-D, it could be shown that each
dimension, x, y, z, could be solved independently and that the resultant quantized
energy would simply be the sum of the separately-obtained quantized energies for
each dimension. In addition, the total wave function would simply be the product
of the separately-obtained wave function for each dimension. [For those interested,
this is a property of the form of the differential equation, i.e., the sum of the
derivatives - relating to the product rule from calculus, etc.] Anyhow, here are the
results - which hopefully make sense to you. Putting it all together for a particle in
a 3-D rectangular box, we have the following. First, the 3-D wave function:
r s r






nx x
ny y
nz z
2
2
2
sin
sin
sin
. (1)
nx ,ny ,nz (x, y, z) =
Lx Ly L z
Lx
Ly
Lz
This can be simplified as follows:
s






8
nx x
ny y
nz z
nx ,ny ,nz (x, y, z) =
sin
sin
sin
.
Lx Ly Lz
Lx
Ly
Lz
Since the volume of the rectangular solid box is merely the product of the three
lengths, we have:
1

(2)

V = volume = Lx Ly Lz ,

(3)

giving:
r
nx ,ny ,nz (x, y, z) =

8
sin
V

nx x
Lx


sin

ny y
Ly


sin

nz z
Lz


.

(4)

Next, the energies. Analogously, the total energy for a 3-D box is merely the sum
of the separate results for each dimension (x, y, and z), i.e., the sum of three 1-D
energies. Similar to the situation with the 3-D wave function, we now have three
quantum numbers, nx , ny , and nz , the quantum numbers for the x, y, and z
dimensions, respectively. In addition, as with the wave function, the length
constraints in the x, y, and z directions are: 0 x Lx , 0 y Ly , 0 z Lz .
Otherwise, each term in the three-term sum has the same form as the 1-D energy
expression derived in lecture. The result is shown below.
Enx ,ny ,nz = Enx + Eny + Enz
n2y h2
n2z h2
n2x h2
+
+
8mL2x 8mL2y 8mL2z

 2
n2y
n2z h2
nx
+
+
=
L2x L2y L2z 8m

(5)

Enx ,ny ,nz =

(6)

Enx ,ny ,nz

(7)

In the case of a cubical box, we have Lx = Ly = Lz L. The result is:


h2
Enx ,ny ,nz = n2x + n2y + n2z
...Cubical Box
8mL2

(8)

Remember what was said in lecture about energy degeneracy, especially in the case
of the cubical box. Distinct combinations of (nx , ny , nz ) give the same quantized
energy. Each distinct (nx , ny , nz ) has its own slot on the energy-level diagram.
Thus, if more than one (nx , ny , nz ) has the same energy, the slots will all be at the
same level on the energy-level diagram. For example, the following quantum
mechanical states will all have the same energy in a cubical box:
(nx , ny , nz ) (2, 1, 1); (1, 2, 1); (1, 1, 2) will all have the same energy, namely:
h2
E2,1,1 = {22 + 12 + 12 } 8mL
2
h2
2
2
2
= E1,2,1 = {1 + 2 + 1 } 8mL
2
h2
2
2
2
= E1,1,2 = {1 + 1 + 2 } 8mL2
6h2
E = 8mL
2.
2

For all three (3) states the energy is the same, i.e., the energy level is said to be
three-fold degenerate.
Some other examples for a cubical box are shown below. Consider the
possible quantum mechanical states that can be constructed from one of the n
values being assigned 1, another 2, and the third 3. The possibilities are:
(nx , ny , nz ) (1, 2, 3); (1, 3, 2); (2, 1, 3); (2, 3, 1); (3, 1, 2) : (3, 2, 1).
They will all have the same energy, namely:
h2
E1,2,3 = {12 + 22 + 32 } 8mL
2
h2
2
2
2
E1,3,2 = {1 + 3 + 2 } 8mL2
h2
E2,1,3 = {22 + 12 + 32 } 8mL
2
h2
2
2
2
E2,3,1 = {2 + 3 + 1 } 8mL2
h2
E3,1,2 = {32 + 12 + 22 } 8mL
2
h2
2
2
2
E3,2,1 = {3 + 2 + 1 } 8mL2
14h2
E = 8mL
2.
For all six (6) states the energy is the same, i.e., the energy level is said to be
six-fold degenerate.
Similarly:
if: (nx , ny , nz ) (1, 1, 1) or (2, 2, 2), each of these are non-degenerate since there
is only one state possible for each energy. The results are:
h2
E1,1,1 = {12 + 12 + 12 } 8mL
2
3h2
E = 8mL2 .
Thus, there is only one state with this energy the (1, 1, 1) state is
non-degenerate.
h2
E2,2,2 = {22 + 22 + 22 } 8mL
2
12h2
E = 8mL2 .
Thus, there is only one state with this energy the (2, 2, 2) state is also
non-degenerate.
2-D Case - Particle in a Corral
If one were to work out the details for the PIB in 2-D, it could be shown that each
of the two dimensions, x and y, say, could be solved independently and the resultant
quantized energy is simply the sum of the separately-obtained quantized energies
for each dimension. Once again, the total wave function is simply the product of
the separately-obtained wave function for each dimension. Here are the results which now hopefully make sense to you. Putting it all together for a particle in a
2-D rectangular corral, we have the following. First, the 2-D wave function:
3

r
nx ,ny (x, y) =

2
Lx

This can be simplified as follows:

s
nx ,ny (x, y) =

2
sin
Ly

4
sin
Lx L y

nx x
Lx

nx x
Lx


sin


sin

ny y
Ly

ny y
Ly


.

(9)


.

(10)

Since the area of the rectangular corral is merely the product of the two lengths, we
have:
A = area = Lx Ly ,

(11)

giving:
r
nx ,ny (x, y) =

4
sin
A

nx x
Lx


sin

ny y
Ly


.

(12)

Next, the energies. Analogously, the total energy for a 2-D corral is merely the sum
of the results for each dimension (x and y), i.e., the sum of two 1-D energies.
Similar to the situation with the 2-D wave function, we now have two quantum
numbers, nx and ny , the quantum numbers for the x and y dimensions,
respectively. In addition, as with the wave function, the length constraints in the x
and y directions are: 0 x Lx , 0 y Ly . As expected, each term in the
two-term sum has the same form as the 1-D energy expression derived in lecture.
The result is shown below.
Enx ,ny = Enx + Eny ,
n2y h2
n2x h2
+
,
8mL2x 8mL2y
 2

n2y h2
nx
+
.
=
L2x L2y 8m

(13)

Enx ,ny =

(14)

Enx ,ny

(15)

In the case of a square corral, we have Lx = Ly L. The result is:

h2

Enx ,ny = n2x + n2y
.
8mL2

(16)

Remember what we mentioned in lecture about energy degeneracy. Now lets

consider the case of the square corral. Distinct combinations of (nx , ny ) give the
same quantized energy. Each distinct (nx , ny ) has its own slot on the energy-level
diagram. Thus, if more than one (nx , ny ) has the same energy, the slots would all
be at the same level on the energy-level diagram. For example, the following
quantum mechanical states would have the same energy in a square corral:
(nx , ny ) (1, 2) or (2, 1).
Both of these states will have the same energy, namely:
h2
h2
2
2
.
E1,2 = {12 + 22 } 8mL
2 = E2,1 = {2 + 1 } 8mL2
5h2
Thus, the two states each have the same energy: E = 8mL
.
2
The above energy is then said to be two-fold degenerate.
Two other examples for a square corral are listed below.
If: (nx , ny ) (1, 1) or (2, 2), each of these states are non-degenerate since there
is only one state possible for each energy. The results are:
2h2
h2
.
E1,1 = {12 + 12 } 8mL
2 E = 8mL2
There is only one state with this energy the (1, 1) state is non-degenerate.
h2
8h2
E2,2 = {22 + 22 } 8mL
.
2 E = 8mL2
There is only one state with this energy the (2, 2) state is also
non-degenerate.
Some advice...Sketch the energy level diagram for the 3-D cube and for the 2-D
square cases. Pay attention to listing the energies in increasing order from lowest to
highest energy. Also, pay attention to degeneracies and note how many energy
slots are present for any degenerate energy level. This should prove extremely
useful when working on the textbook problems - listed at the end of this document.
Addendum - Probabilities: Integrals and Areas Under Curves...
Recall the quantum mechanical postulate that the square of the wave function,
|(x, y, z)|2 , is the probability density that the described particle is found at
location (x, y, z). Since this is a probability density, a probability per volume, one
must evaluate it over a chosen volume in order to obtain an actual probability, i.e.,
to obtain a fraction between 0 and 1.
Since any
function is normalized, the integral over all space is one
R Rwave
R
1=
|(x, y, z)|2 dx dy dz. To make this a little less abstract, we will
V olume
apply all of this specifically to the 1-D PIB.
Lets return for a moment to the bead-on-a-string, i.e., the particle in a 1-D box.
The probability of finding the bead between any two points a Rand b on the
b
string between 0 and L should be given by: P rob.(a x b) = a n2 (x) dx. Lets
5

Rb
think about this for a moment. The integral: a f (x) dx is the area under the curve
of a plot of f(x) versus x between points x = a and x = b. So - at least for the 1-D
n (x) PIB wave functions - we can easily sketch the probability density n2 versus
x. Sometimes, by merely looking at the sketch we can - by its symmetry and the
knowledge that the total area must be one - determine the desired probability
without analytically calculating the integral.. Try the textbook PIB problems They
are listed below for reference.
Recall the textbook problems from Chapter 12 of Zumdahl, Chemical
Principles Chemistry 6/e. The Particle-in-a-Box Chapter 12 problems are:
46 through 51 - page 585.
Additional Problems: 128, 133, 136, and 137 - pages 589 - 590.
4 problems. Give them a try.