Symbolic Math Approach to Solve Particle-in-the-Box

and H-atom Problems

Todd M. Hamilton, Ph.D
Department of Chemistry
Georgetown College
Georgetown, KY 40324
Todd_Hamilton@georgetowncollege.edu
Copyright 2006 by the Division of Chemical Education, Inc., American Chemical Society. All rights reserved. For
classroom use by teachers, one copy per student in the class may be made free of charge. Write to JCE Online,
jceonline@chem.wisc.edu, for permission to place a document, free of charge, on a class Intranet .
Goal
This exercise is designed to give undergraduate physical chemistry students a "hands-on"
experience in solving the hydrogen atom. The students explore a step-by-step solution to the
Schrdinger equation in a symbolic way and explore properties of the radial wavefunction.
Objectives
Upon completion of the exercise students should be able to:
1. solve for the energy of the particle in a box symbolically
2. solve the Schrdinger equation symbolically for the energy of the hydrogen atom
3. explain how a wavefunction is normalized
4. discuss the features of the 1s radial wavefunction for the hydrogen atom
5. explain how the size of the 1s orbital is determined
6. solve for the energy of the one-dimensional harmonic oscillator symbolically
Prerequisites
This exercise is intended for junior-level students who have been introduced to quantum
mechanics, particularly the particle-in-a-box problem. Two semesters of calculus and a
semester of physics is desired. Students should also have some experience working with
derivatives and integrals in Mathcad.
References
1. Levine, I. N. Quantum Chemistry, 5th Edition, Prentice Hall, 2000.
2. Levine, I. N. Physical Chemistry, 5th Edition, McGraw-Hill, 2002.
3. Hanson, D. M. and Zielinski, T. J. Quantum States of Atoms and Molecules, CD-ROM, 2001.
4. Newhouse, P. F. and McGill, K. C. J. Chem. Educ. 81, 424 (2004).
5. Mak, T. C. W. and Li, W. J. Chem. Educ. 77, 490 (2000).
6. Turner, D. E. J. Chem. Educ. 70, A185 (1993).
7. Lain, L., Toree, A., and Alvarino, J. M. J. Chem. Educ. 58, 617 (1981).
8. Peterson, C. J. Chem. Educ. 52, 92 (1975).
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Todd M. Hamilton
Page 1
Introduction
The Schrdinger equation can be solved exactly for the hydrogen atom. After some practice with
the particle in a box problem, you will solve the H atom symbolically using the derivatives feature in
MathCad. The result is an expression for the energy levels of the hydrogen atom. You will also
prove that the radial part of the wavefunction is normalized and explore the concept of an orbital.
The Schrdinger equation in spherical coordinates for the H atom is as follows:
h
2

2 r
2

r
r
2
r

d
d

\
|
.
d
d
1
sin
|

\
|
.
sin

d
d

\
|
.
d
d
+
1
sin
2

\
|
.
2

d
d
2
+

(
(
(

Z e
2

r
|

\
|
.
= E
where h is actually h-bar (h divided by 2), is the wavefunction, is the reduced mass, Z is
the atomic number, e is actually e-prime (e divided by sqrt(4
0
)), and E is the function for
the allowed energy levels. The e
2
term is the Coulomb potential energy function.
After a separation of variables, the radial part of the Schrdinger equation can be set equal to
a constant, :
h
2
R r ( ) r
r
2
r
R r ( )
d
d

\
|
.
d
d

(
(

2 r
2

R r ( )
E
Z e
2

r
|

\
|
.
+

(
(

R r ( ) + =
where R(r) is the radial wavefunction and = ( +1). For an s orbital, =0 and =0. After setting
= 0 and a little algebra, the Schrdinger equation becomes:
r
r
2
r
R r ( )
d
d

\
|
.
d
d

(
(

2 r
2

h
2
Z e
2

r
|

\
|
.
R r ( ) + =
2 r
2

h
2
E R r ( )
After defining the radial wavefunction R(r), you will perform the derivatives in the first part
of the equation. Then you will add in the potential energy term. Finally, you will isolate the
energy function. In this exercise, we are focusing only on the radial wavefunction for the 1s
orbital (n=1) in order to simplify the mathematics.
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Todd M. Hamilton
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A. Practice with the Particle in a Box
Before you tackle the H atom, you will obtain some practice solving the particle in a box (PIB).
The wavefunction for the PIB is as follows:

2
A
|

\
|
.
1
2
sin n
x
A

\
|
.
:= n
The Schrdinger equation for the PIB is very simple (with the potential energy V=0):
2
x

d
d
2
=
2 m
E
h
2
|

\
|
.
2

where m is the mass of the particle, h is Planck's constant, and E is the allowed energies of
the particle. Begin by taking the derivative of the wavefunction (select the expression below
and hit Ctrl+period, then enter). You should get a cosine function as the result.
x

d
d
Now try the second derivative of the wavefunction below. You should get the original
wavefunction back (in fact this a requirement for solving the Schrdinger equation) times
some constants.
2
x

d
d
2
Now, divide the result from the second derivative by -2m/(h/2)
2
(see the Schrdinger
equation above) to isolate the E function. To do this, copy and paste your latest result into
the little black box below (or retype the result). Click outside of the math area, then back
inside, hit Ctrl +period, then enter:
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Todd M. Hamilton
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2 m

h
2
|

\
|
.
2

The answer should be E=n

2
h
2
/(8ma
2
)
Since the particle has a 100% probability of being found somewhere in the box, that is with an x
value somewhere between 0 and a, the integral of the probability density function
2
between
x= 0 and x = A must be equal to 1. To assure this we write the wave function for the particle as
(x) = N sin(nx/A), where N is called the normalization constant, and then determine the value
of N that will make
0
A
x
2
x ( )

d 1 =
We will use Mathcad's ability to solve equations symbolically to to determine the value of the
normalization constant. Below is the equation for the integral of
2
with written out as
N sin(nx/A).
0
A
x N sin
n x
A
|

\
|
.

\
|
.
2

(
(
(

d 1 =
Copy this equation into the space below. Important: Since n must be a positive integer, replace
n with any positive integer before completing the next steps.
Next:
1. Click in the space between the left parenthesis and the N so that N and only N is enclosed in
the blue selection L.
2. Go to the symbolics menu on the tool bar, click on variable, then click on solve.
This tells Mathcad to solve for the value of N that will make the integral equal to 1. Notice that
you get two solutions, one positive and one negative. Only the positive value is meaningful.
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Replace your original choice for n with another integer and repeat steps 1 and 2. Notice that you
get exactly the same solution(s) for N. For the particle in a box the normalization constant is the
same for all states (all values of n). Can you simplify the expression Mathcad gives for N into a
more familiar form?
The PIB wavefunction is normalized. In other words, the integral of
2
over the box
length a is equal to 1 (see below). Change the upper limit of integration by changing
the variable "factor" below (try 2 for half the box, 3 for one-third of the box, etc.). After
changing the upper limit, try different n values by changing the n value below (try 2, 3, 4,
etc.) Also, notice how the graphs below change for different n values.
factor 1 := A 1 := n 1 := c
n
A
:=
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0
A
factor
x
2
A
|

\
|
.
sin c x ( ) sin c x ( )

(
(

d 1 =
0 0.5 1
2
0
2
2
A
|

\
|
.
1
2
sin c x ( )
x
=
0 0.5 1
0
1
2
2
A
|

\
|
.
sin c x ( ) sin c x ( )
x

2
=
B. The Solution to the Hydrogen Atom
The general form of the radial wavefunction is a byproduct of solving the Schrdinger
equation. We will restrict ourselves to the 1s orbital to simplify the mathematics. The
radial wavefunction for the 1s orbital in the hydrogen atom is R(r) = 2(Z/a)
3/2
e
-Zr/a
.
where a is a constant with dimensions of length (a = 0.5295 ).
1. Type in the wavefunction in the space below.
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R:=
2. Take the first derivative of the wavefunction with respect to r (copy and paste in the
wavefunction that you typed in above):
r
d
d
3. Next, multiply the result by r
2
and take the derivative again.
r
r
2

( )
d
d
4. Now you are ready to add in the potential energy term. The full term is:
2 r
2

h
2
Z e
2

r
|

\
|
.
R r ( )
where Ze
2
/r is the Coulomb potential energy function.
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However, the symbolic solution is easier to find if we combine some terms. For example, if
we note that the constant a = h
2
/e
2
, we can rewrite the above term as
2 Z r R
a
. Add this
term to the latest result and evaluate. If you have trouble copying and pasting the result to
the right of the evaluation arrow, copy the terms to the left of the arrow instead.
2 Z r R
a
+
5. As shown above in the Introduction, the current result is equal to
2 r
2

h
2
E R r ( )
Divide your result by
( )
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2 r
2
R r ( )
( )
h
2
to obtain E, the energy function for the 1s orbital in the hydrogen atom.
2 r
2
R
h
2
Notice that this function contains only one parameter - the atomic number, Z - and is
applicable to hydrogen-like atoms as well. For the H atom, the ground state energy
level is -13.6 eV. The n=2 level requires a different (more sophisticated) wave function
to solve the Schrdinger equation.
In the calculation of the 1s energy level below, change the Z value from 1 (for H) to a higher atomic
number to calculate the energy levels for hydrogen-like atoms. Try uranium!
Z 1 :=
Created March 2005
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J/eV (conversion factor from Joules to electron volts)
angstroms
J
kg
eV
JpereV 1.602177 10
19
:=
a 0.529466 10
10
:=
h
6.62608
2 3.1416
10
34
:=
9.10443 10
31
:=
E =
1
2
Z
2
a
2

h
2
JpereV
13.598 =
C. Normalization of the H Atom Wavefunction
You will now prove that the radial wavefunction for the 1s orbital in the hydrogen atom is
normalized. First, square the radial wavefunction. The wavefunction is provided below to aid
in the process; type in the expression for the squared wavefunction.
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Z 1 :=
R 2
Z
a
|

\
|
.
3
2
exp
Z r
a
|

\
|
.
:=
r
R
2
:= R
2
Next, multiply the squared wavefunction by r
2
and integrate over dr. The factor of r
2
takes into
account the fact that you are integrating the volume inside a surface located at a distance r
from the nucleus. Note that you are integrating from 0 to infinity. Again, if you have trouble
with copying and pasting, simply enter "R
2
" into the integral below.
0

r r
2

d
Examine the results. Is the radial wavefunction for the H atom normalized?
D. Plotting the H Atom Wavefunction
Plot the radial wavefunction R versus r for Z=1 (copy and paste the radial wavefunction
R into the box on the y-axis). Set the y-axis limits to (0,2) and the x-axis limits to
(0,5).
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a 1 :=
Z 1 :=
Now plot the square of the radial wavefunction R
2
, times r
2
, versus r (put the r
2
factor
at the end of the R
2
equation). Set the y-axis limits to (0,0.6) and the x-axis limits to
(0,5).
E. Orbitals
The integral of the function that you just plotted is equal to the probability of finding the
electron at a particular distance from the nucleus. Orbitals illustrated in textbooks usually
define the surface of the orbital at the distance r which contains 90% of the electron
probability. In the active region below, the upper limit is in multiples of the constant a
(remember a is approximately 0.53 ). You see that a sphere of radius equal to the
constant a contains about 32% of the probablility. Change the upper limit of integration
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Todd M. Hamilton
Page 12
until the sphere contains 90% of the probability (until the integral evaluates to exactly 0.9).
a 1 :=
Z 1 :=
upperlimit 1 :=
0
upperlimit
r 4
Z
a
|

\
|
.
3
e
2 Z
r
a

r
2

(
(
(

d 0.323 =
The upper limit value that you just found is the radius (as a multiple of a) that contains
90% of the electron probability. This is the size of the 1s orbital usually displayed in
textbooks. Find approximately where this radius is on the plots above (in Section D).
You have defined the surface of the 1s orbital of the H atom.
How far out must you integrate to get essentially 100% of the probability (until the integral
evalutes to exactly 1)?
F. Mastery Exercise
The Schrdinger equation for the One-Dimensional Harmonic Oscillator is as follows:
2
x

d
d
2
+ 2 m E h
2

2
x
2

( )
= 0
where = 2m/h, h is actually h-bar, and m is the mass of single particle attracted toward the
origin by a force proportional to the particle's displacement from the origin:
Created March 2005
Updated August 2005
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Todd M. Hamilton
Page 13
F
x
= -kx
The force constant, k, is related to the vibrational frequency, , as follows:
= (1/2)(k/m)
1/2
The first two wavefunctions that solve the Schrdinger equation are:

0
=

\
|
.
1
4
e

x
2
2

1
=
4
3

\
|
.
1
4
x e

x
2
2

Show that these wavefunctions solve the Schrdinger equation for the One-Dimensional
Harmonic Oscillator and state the energies of the first two levels. You will rearrange the
Schrdinger equation to solve for the energy (similar to what was done for the H atom).
Important note: open a new window to solve this section.
Also, plot the wavefunctions and prove that they are normalized (set = 1 for the purposes of
plotting and normalization). Remember to integrate from - to + .
Created March 2005
Updated August 2005
Updated February 2006
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Todd M. Hamilton
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Created March 2005
Updated August 2005
Updated February 2006
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