In the Classroom

edited by
Advanced Chemistry Classroom and Laboratory Joseph J. BelBruno
Dartmouth College
Hanover, NH 03755

Intuitive Solution to Quantum Harmonic Oscillator at Infinity

Cory C. Pye
Department of Chemistry, Saint Mary’s University, Halifax, NS Canada B3H 3C3; cory.pye@stmarys.ca

Over the course of the last few years, the author has ex- At this point, it is traditional to examine the behavior at in-
pended considerable effort into developing the laboratory finity of this differential equation by examining the slightly
component of a one-semester quantum chemistry course at simpler differential equation:
Saint Mary’s University. The approach the author has taken
is to allow the students to solve the “big” problems in quan- d 2ψ 2
tum chemistry by subdivision into smaller problems that can 2
− ξ ψ(ξ) = 0 (7)
dξ
be independently tackled by a student with a two-year cal-
culus background. Some examples of the big problems solved Approximate solutions to eq 7 are usually given without deri-
by the students are the derivation of the Rayleigh–Jeans and vation or plausibility arguments as:
Planck’s law, the harmonic oscillator (classical and quantum),
the radial equation of the hydrogen atom, the derivation of 2
ξ
the Laplacian in spherical polar coordinates, the solution of ψ ( ξ ) = exp ± (8)
the associated Legendre equation, and a particle in a semi- 2
infinite box. In the process of creating these labs, the author
has combined intuition and rigor in order to build on the After eliminating the positive exponent and assuming the
solution to eq 6 as having the form,
students’ mathematical skills and has found intuitive dem-
onstrations of previously “assumed” results. 2
The solution to the quantum harmonic oscillator prob- ξ
ψ ( ξ ) = H ( ξ ) exp − (9)
lem is widely discussed in elementary quantum mechanics 2
texts (1–8) and in this Journal (9). The Schrödinger equa-
tion applied to the harmonic oscillator is, one then proceeds to show that the power series H(ξ) must
truncate to give the Hermite polynomials.
h 2 d2 ψ 1 The solutions, eq 8, once given, are relatively easy to
− + kx 2 ψ ( x ) = E ψ( x ) (1) verify as approximate solutions to eq 7. However, it is not
2µ dx 2 2 immediately obvious why they have the form that they do.
The approach taken in ref 9 is actually incorrect. One can
where ប is Planck’s constant divided by 2π, µ the reduced
mass, k the spring constant, x the displacement, E the en- recast eq 7 in operator form,
ergy, and ψ the wavefunction. After suitable algebraic ma-
nipulation, we obtain ( D 2 − ξ2 ) ψ = 0 (7a)

d2 ψ but this is not the same thing as,

dx 2
( )
+ λ − α2 x 2 ψ ( x ) = 0 (2)
(D + ξ)(D − ξ)ψ = 0 (7b)
where
because D and ξ do not commute (they are operators corre-
2 µE sponding to essentially momentum and position). Equation
λ = (3)
h
2 7b actually expands into,

and:
1
( D 2 + ξD − Dξ − ξ2 ) ψ = 0 (7c)
kµ 2
α = 2 (4) where the middle two operators do not cancel. However, the
h solutions to eq 7b are the approximate solutions of eq 7. What
follows is a simple, intuitive approximate solution to eq 7.
Linear scaling of the independent variable by,

ξ = αx (5) Solutions at Infinity

gives: Equations 6 and 7 state that taking the second deriva-

tive of a function gives the same function back times another
d 2ψ λ (rather simple) function. Although the exponential function
+ − ξ2 ψ (ξ) = 0 (6)
dξ 2 α itself does not satisfy eq 7, it suggests that we try a related

830 Journal of Chemical Education • Vol. 81 No. 6 June 2004 • www.JCE.DivCHED.org

 In the Classroom

function as a trial solution, namely: n = 2, to get:

ψ ( ξ ) = exp 
 f ( ξ ) 
 (10) (
2a + 4a 2 − 1 ξ2 = 0 ) (18)

The first two derivatives of this trial function are The second order term will disappear if 4a2 − 1 = 0, that is,
a = ±1兾2. This can be shown by dividing eq 18 by ξ2 and
dψ df taking the limit as ξ → ∞. Substituting the values for a and
= exp 
 f ( ξ )
 (11)
dξ dξ n back into eq 15, and this result back into eq 10, gives the
desired result, eq 8.
and In principle, one can apply the same argument to eq 6
directly, which gives:
2
d 2ψ df d2 f
 f ( ξ ) 
= exp   dξ  f ( ξ ) 
+ exp   (12) λ
dξ 2 dξ 2 2a +
α
(
+ 4a 2 − 1 ξ2 = 0 ) (18a)
Substituting eq 12 into eq 7 gives:
The same result follows and, in addition, one can obtain the
energy of the n = 0 level by solving,
2
df d2 f
 f ( ξ ) 
exp   d ξ  f ( ξ ) 
+ exp   1 λ
dξ 2 2 − + = 0 (18b)
(13) 2 α
2
 f ( ξ ) 
− ξ exp   = 0 without the need to discuss approximate solutions at infinity.

The exponential factor multiplying all terms is never zero, Acknowledgments

and therefore we may divide through to get:
I would like to thank the Chemistry 412 (quantum
2
chemistry) students of 1999–2002 at Saint Mary’s Univer-
d2 f df 2 sity for working through the labs described above and cor-
+ − ξ = 0 (14)
dξ 2 dξ recting many errors in the early versions.

We have converted a linear differential equation to a nonlin- Literature Cited

ear one, for which the theory is more complicated and gen-
eral techniques for solving them are lacking (10). However,
the simple form of eq 14, in spite of its nonlinearity, sug-
gests that a polynomial may work. We use a trial function,
f ( ξ ) = a ξn
to obtain:
n ( n − 1) a ξn − 2 + n2 a 2 ξ2 n − 2 − ξ 2 = 0
The order of the highest term, and thus the one dominating
as ξ → ∞, is given by:

2n − 2 if n ≥
2 8. Ratner, M. A.; Schatz, G. C. Introduction to Quantum Me-
max ( 2n − 2, n − 2, 2 ) = 

2 if n ≤
2 (17) chanics in Chemistry; Prentice-Hall: Upper Saddle River, NJ,
We note that if n = 2, the first term of eq 16 is constant and
the second and third terms are both second order, which im-
plies that they could cancel (i.e., the differential eq 14 can
have an approximate solution for large ξ). We therefore take
1. Eyring, H.; Walter, J.; Kimball, G. E. Quantum Chemistry;
Wiley: New York, 1944; pp 75–79.
2. McQuarrie, D. A. Quantum Chemistry; University Science
Books: Mill Valley, CA, 1983; pp 175–177.
3. Eisberg, R.; Resnick, R. Quantum Physics of Atoms, Molecules, Sol-
(15) ids, Nuclei, and Particles, 2nd ed.; Wiley: New York, 1985, p I2.
4. Dykstra, C. E. Introduction to Quantum Chemistry; Prentice-
Hall: Englewood Cliffs, NJ, 1994; p 35.
5. Griffiths, D. J. Introduction to Quantum Mechanics; Prentice-
(16)
Hall: Upper Saddle River, NJ, 1995; pp 37–43.
6. House, J. E. Fundamentals of Quantum Mechanics; Academic
Press: San Diego, CA, 1998; pp 112, 119.
7. Levine, I. N. Quantum Chemistry, 5th ed.; Prentice-Hall: Up-
per Saddle River, NJ, 2000; pp 67, 90.
2001; pp 73–78.
9. Dushman, S. J. Chem. Educ. 1935, 12, 381–389.
10. Boyce, W. E.; DiPrima, R. C. Elementary Differential Equa-
tions and Boundary Value Problems, 4th ed.; Wiley: New York,
1986.

www.JCE.DivCHED.org • Vol. 81 No. 6 June 2004 • Journal of Chemical Education 831