Research: Science and Education

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

Variational Principle for a Particle in a Box

Juan I. Casaubon
Facultad de Ciencias Exactas y Naturales, Universidad de Belgrano y CONICET, Villanueva 1324, 1426 Buenos Aires,
Argentina

Graham Doggett*
Chemistry Department, University of York, Heslington, York YO10 5DD, UK; gd1@york.ac.uk

The particle in a one-dimensional infinite square well Introduction of a Basis Set

potential provides one of the simplest quantum mechanical
model systems, in which the potential is constant in a box of
length L. The position of the particle, x, may be defined with
respect either to the left-hand edge of the box, 0 ≤ x ≤ L, or
to the center of the box,
L/2 ≤ x ≤ L/2. This “particle-in-a-
box” (PIB) model is widely used as an example in teaching
chemistry undergraduates the derivation and properties of the
solutions of the Schrödinger equation (1, 2). The PIB system
also provides a very good paradigm for motivating the uses
of the variational principle, symmetry constraints, and the
concept of a basis set.
The next section contains a brief summary of the equa-
tions associated with the variational principle, when a linear
combination of functions is used to model the exact wave
function. Subsequent sections describe how suitable approximate
wave functions with zero, one, or two variational parameters may
be formulated with and without imposing the requirements of
symmetry. A new form of one-parameter wave function is also
described. Results are obtained for several approximations for
the first three energy states, using polynomial basis functions
up to degree four, and links are made with the work of
Bransden and Joachain (3).
The Variational Method
In the Rayleigh–Ritz variational method (1, 3, 4), the
trial function χ var is used to evaluate the expectation value,
ε var, of the Hamiltonian,
:
χ var
χ var
εvar = (1)
χ var |χ var
The optimum forms for χ var are obtained by minimizing
ε var with respect to the n parameters contained in χ var, a pro-
cedure which yields n values for ε var, with the upper-bound
property for each one that ε k ≥ Ek (k = 1, 2, …, n). Different
choices of χ var may be made; if there are no variation param-
eters, then the energy is obtained directly from eq 1. In the
case of a trial function depending upon an adjustable param-
eter, ξ, say, the optimum value of ξ is obtained by solving
∂εvar
=0 (2)
∂ξ
after using eq 1 to evaluate the energy. The question of con-
structing suitable approximate wave functions is best accom-
plished through the introduction of a basis set, as described
in the next section.
If the model wave function χ var is expressed as a linear
combination of r suitably chosen basis functions, φ k,
r–1
χvar = Σ a k φk (3)
k=0
then the ak are the variational parameters, and the (known)
expansion functions, φ k , may be neither normalized to unity
nor orthogonal. For any choice of r suitable basis functions
then, as already noted, r upper bounds, ε k, are expected.
To carry out the variational approach, the substitution of
eq 3 into eq 1 and the use of r conditions analogous to eq 2,
but with each of the ak values in turn replacing ξ , leads to
the secular determinant (eq 4) for the energies:
|H – ε S| = 0 (4)
and the secular equations (eq 5) for the coefficients
r–1
Σ
H k t – εS k t a t = 0; k = 0, 1, 2, …, r – 1 (5)
t=0
The energy and overlap integrals Hkt and Skt , respectively, have
the properties Hkt = Htk =
φk|
|φt and Skt = Stk =
φk|φt.
For the PIB problem, the exact energies, in atomic units,
are
n2 π 2
En = ; n = 1, 2, 3, … (6)
2mL
2
where m is the mass of the particle (for an electron, m = 1),
and the associated eigenfunctions are
Ψn = 2 sin nπ x
(7)
L L
for 0 ≤ x ≤ L.
Choice of Basis Functions, φ k
In general, the basis functions, φk, may be chosen to be
eigenfunctions of part of the Hamiltonian operator, or of a
model operator (as in the SCF method), or, in Dewar’s words
(5), we can “choose the basis functions in any way we please,
guided by intuition, prayer, or any other suitable source of
inspiration’’. In this work, different sets of basis functions are
used, in which the individual members are built out of (non-
orthogonal) monomials of the form x k (k = 0, 1, 2, …).
The most general polynomial form of degree r, for the
approximate PIB wave function, is given by
χvar = a0 + a1x + a2x2 + … + ar x r (8)

JChemEd.chem.wisc.edu • Vol. 77 No. 9 September 2000 • Journal of Chemical Education 1221

 Research: Science and Education
which has r + 1 terms, irrespective of the choice of origin for
the position coordinate. However, in order that χvar be an
acceptable model wave function for the PIB problem, it must
satisfy the same boundary conditions as the exact solution:
that is, χvar(0) = 0 and χvar(L) = 0, if the coordinate origin is
taken at the left-hand box edge. These boundary conditions
require that a0 = 0 and a1 =
a2L – a3L2 – a 4L3 – … – ar Lr –1,
respectively. Thus, χvar takes the form
χvar = x(x – L){c1 + c2(x + L) + c3(x2 + xL + L2) + … + cr–1Gr–1(x,L)} (9)
in which ck = ak+1, and
k
Gk x, L = Σ x k–s L
s–1
s=1
The Gk polynomials have the property
G1(x,L) = 1; Gk+1(x,L) = xGk(x,L) + Lk; k = 1, 2, …
and two degrees of freedom have been lost from the uncon-
strained expansion of eq 8. The original basis of r + 1 mono-
mials therefore reduces to a new basis of r – 1 functions of
the form
φk = x(x – L)Gk(x,L); k = 1, 2, …, (r – 1)
and the expansion (eq 9) becomes
χvar = c1 φ1 + c2 φ 2 + … + cr–1 φr–1
An expansion of the form of eq 11 acts as a paradigm
for the solution of the secular problem for three-dimensional
systems where, in the case of atoms or molecules, for example,
the expansion could be made using Slater-type atomic orbitals
or Cartesian Gaussian functions (usually centered on the
nuclei) (6 ) as the basis functions, φk . The only real difference
between the PIB model system and an atom or molecule
(assuming the clamped nucleus approximation) lies in the
complexity and number of the energy integrals Hkt : boundary
conditions and spatial symmetry requirements are common
to all problems.
The normalization requirement and symmetry constraints,
if imposed, will lead to a further loss of degrees of freedom.
A Model Wave Function with no Variational Parameters
It follows from the above discussion that the simplest
acceptable approximate wave function can possess only one
basis function and is therefore represented by the quadratic
polynomial
χvar = Nφ1 = Nx(x – L) (12)
where N is determined by the normalization requirement

χvar| χvar = 1.
This choice of wave function, in which χvar < 0 for 0 <
x < L, stems from the definition of φk in eq 10; however, the
sign of the φk may be changed if desired—without loss of
generality—to ensure that χvar > 0. The model wave function
in the form of eq 12, described by Levine (1) and Besalú and
Marti (2), possesses no variational parameters, and yields an
energy of
ε1 = 5 2
mL
with an error of 1.3% relative to the exact energy E1.
1222 Journal of Chemical Education • Vol. 77 No. 9 September 2000 • JChemEd.chem.wisc.edu
The Symmetry of the Ground State Wave Function
Under inversion, the point x is transformed into the point
L – x and vice versa, leaving χvar invariant. The wave function
(eq 12) is therefore even (g) under inversion. This property
is more apparent if the coordinate origin is transferred to the
center of the box, using the substitution x → x + L/2:
χvar → N(x + L/2)(L/2 – x) = M(x 2 – α2) (13)
where α = L/2. In this coordinate system, x →
x under in-
version, and the invariance of eq 13 is obvious.
If the PIB problem is solved using the box center as origin,
then it is appropriate to constrain χvar to be expanded over
either even or odd monomials, x k, and also to satisfy the
boundary conditions χvar(±α) = 0. In this situation, the ex-
pansion functions φk are given by (x 2 – α2)Gk(x 2, α2) (even
parity), and xGk(x 2, α2) (odd parity).
One-Parameter Model Wave Functions
If one degree of freedom is required, this is achieved by
working with two basis functions of the form of eq 10, as is
seen in eq 9:
(10)
χvar = x(x – L){c1 + c2(x + L)} (14)
But, since the c2L term in the braces is independent of x, the
(11) wave function (eq 14) may be written in the equally accept-
able form
χvar = Mx(x – L){1 + cx}
where c = c2 /(c1 + Lc2) and M is a constant. The optimization
of c leads to a secular determinant (eq 4) of order two, with
roots
ε1 = 5 2 , ε2 = 21 2
5mL 5mL
There is thus no improvement to the ground state, but an
upper bound, ε2 (with a 6% error), is now obtained for the
first excited state (odd parity), with wave function given by
χvar = Nx(L –2x)(x – L) = M{LG1 – 2⁄3G2}
or χvar = Nx(x2 – α2) when transforming the origin to the
center of the box. It is clear, therefore, that the extra degree of
freedom has permitted the second energy state to be accessed
without any corresponding improvement in the ground state—
a direct consequence of the effects of symmetry, since the
ground state can be improved only through the inclusion of
the monomial x4 (i.e., three basis functions are required).
However, it is possible to improve the ground state energy
by working with a different quadratic form for the wave func-
tion, as is seen in the next section.
A New Ground State One-Parameter Wave Function
Consider the following well-behaved function, depend-
ing upon the one parameter ξ
0≤x ≤ξ

M L – 2ξ x
χvar = M
ξ2 + x L – x ξ≤x ≤L –ξ
(15)
M L – 2ξ L – x L –ξ≤x ≤L

The energy of χ var and the derivative of the energy with
respect to the variational parameter ξ are as follows:
3 2 3
5 16ξ – 12ξ L + L
εvar = m

32ξ5 + 40ξ4L – 10ξ2L 3 + L 5
(16)
2 2
∂εvar 1 40ξ 16ξ + 4ξL – L
=
∂ξ 2m 2 built up from n suitably scaled and oriented contiguous segments

8ξ3 + 2ξ2L + 4ξL 2 + L 3
The derivative is zero for ξ = 0, 0.15451L,
0.40451L. The
value ξ = 0 corresponds to the previous approximate wave
function (eq 12); ξ = 0.15451L yields a ground state energy
of 4.9442/mL2 , with an error reduction from 1.3 to 0.19%.
The negative solution has no physical significance.
The Bransden and Joachain Approximation for χvar
Bransden and Joachain (3) used the following fourth-
degree polynomial to model the ground state of the PIB prob-
lem (origin of coordinates at the box center):
χvar = N(α2 – x2)(1 + cx2) (17)
where c is the variational parameter and α = L/2. As seen above,
this even-parity wave function is built from the two basis
functions (α 2 – x 2)G1(x 2, α 2) and (α 2 – x 2)G2(x 2, α 2), and
provides upper bounds to E1 and E3.
On using eq 17 in eqs 4 and 5, two values for c are ob-
tained: one corresponding to the ground state (n = 1), with
no nodes in (0, L) and energy (0.0015% error)
ε1 = 4.934875
2 2
mL
and the other to the second excited state (n = 3), with two
nodes in (0, L) and energy (14% error)
ε3 = 51.065
mL 2
If a trial function of odd parity is taken by multiplying
eq 17 by x , an upper bound for the n = 2 state may be found,
as suggested in Problem 8.17 of Bransden and Joachain (3).
The same values of ε1, ε2, and ε3 are obtained using χvar
expanded over the first three basis functions, x(x – L)Gk(x,L),
for k = 1, 2, and 3:
χvar = x(x – L){c1G1 + c2G2 + c3G3} =
x(x – L){c1 + c2(x + L) + c3(x 2 + xL+ L2)} =
Mx(x – L){1 + cx + c′x(L + x)}
where c = c2/(c1 + c2L + c3L2) and c′ = c3/(c1 + c2L + c3L2).
Use of Symmetry
If the x(x – L)Gk(x,L) basis functions are used to describe
χvar, symmetry-adapted wave functions can be constructed be-
fore using the variational principle by applying the projection
operators (1+ î), (1 – î), where î is the inversion operator, to
obtain even or odd wave functions, respectively. However,
by avoiding the use of symmetry-adapted expansions, selected
even and odd states can be accessed in a single calculation.
JChemEd.chem.wisc.edu • Vol. 77 No. 9 September 2000 • Journal of Chemical Education
Research: Science and Education
Thus, for r basis functions it is possible to determine upper
bounds to r /2 even states and (r – 2)/2 odd states (r even)
and (r – 1)/2 even and (r – 1)/2 odd states (r odd).
Use of a Ground State Wave Function to Model
Excited States
If the model wave function for the ground state (n = 1)
is written as ψ1(x,L), which is equivalent to χvar(x,L), the wave
function for the state with quantum number n, χvar may be
derived from ψ1 —each of which is defined in a box segment of
length L/n. Thus, for the second excited state (n = 3), for ex-
ample, the box is divided into three segments of length L/3,
and the model excited state wave function takes the following
forms in the three segments:

ψ1 x, L/3 0 ≤ x ≤ L/3
χvar x,L =
ψ1 x – L/3, L/3 L/3 ≤ x ≤ 2L/3
ψ1 x – 2L/3, L/3 2L/3 ≤ x ≤ L
In the general case, χvar is constructed from the n segment
wave functions
i –1 L

1 ψ1 x –
i–1
n , L/n , i = 1, 2, 3, …, n
It is now easy to show that the two integrals in the numerator
and denominator of the expression for the expectation value of
the Hamiltonian (eq 1) reduce to n3 and n times, respectively,
the contributions obtained from ψ1(x,L). Hence eq 1 reduces to
n 2K
εn = , n = 1, 2, 3, …
mL
where K = mL 2 ε1. Thus, in the calculations reported here,
values of K = 5, 4.9442, 4.934875 were obtained, with the
ground state wave functions of eqs 12, 15, and 17, respec-
tively. However, as the approximate ground state wave func-
tion is improved in quality, K → π 2/2 (see eq 6); that is K →
4.934802.
Conclusion
The solution of the particle-in-a-box problem is shown to
provide a useful quantum chemical paradigm for demonstrat-
ing the use of the variational principle. In this investigation, the
approximate wave functions for ground and excited states are
expanded in terms of a basis of monomials, x r. The secular
determinant and associated equations may be solved easily,
using Maple or Mathematica, for example, to compare the
calculated energies and wave functions for basis set expansions
of increasing size. The analysis given here may be readily
adapted to form a class exercise for computer-literate under-
graduates, and is a useful model system for illustrating the
procedural basis for understanding the solution of more
advanced electronic structure calculations. The wave functions
produced can also be characterized by their even/odd sym-
metry characteristics under inversion, and the notion of a
symmetry projection operator can be introduced. Finally, a
different model for the PIB system is introduced, which
permits the construction of excited state wave functions from
1223
 Research: Science and Education

suitably scaled and signed segmented functions built from a
model ground state wave function (a piecewise wave function).
Literature Cited
1. Levine, I. N. Quantum Chemistry; Prentice-Hall: Englewood
Cliffs, NJ, 1991.
2. Besalú, E.; Martí, J. J. Chem. Educ. 1998, 75, 105.
3. Bransden, B. H.; Joachain, C. J. Introduction to Quantum
Mechanics; Longman: Harlow, UK, 1989.
4. Winter, R. G. Quantum Physics; Faculty Publishing: Davis, CA,
1986.
5. Dewar, M. J. S. The Molecular Orbital Theory of Organic
Chemistry; McGraw-Hill: New York, 1969.
6. Davidson, E. R.; Feller, D. Chem. Rev. 1986, 86, 681.

1224 Journal of Chemical Education • Vol. 77 No. 9 September 2000 • JChemEd.chem.wisc.edu