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The Chemical Educator

Perturbation Theory for a Particle in a Box

Henry E Montgomery Jr, William P. Crummett

Published Mar 21, 2005• 0 citations
Publisher

Abstract

Rayleigh–Schrödinger perturbation theory is used to find energy and wavefunction corrections for a particle confined in a box with infinite walls. The resulting perturbation equations have simple, analytic solutions. The procedure for normalization of the wavefunction corrections is demonstrated, and the perturbation energies and normalized wavefunctions are shown to approach the exact values. The method is applied to both the ground state and first excited state and can become a valuable component of a student’s introduction to perturbation analysis.

DOI
10.1333/s00897050896a

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Rayleigh–Schrödinger perturbation theory is used to find energy and wavefunction corrections for a particle confined in a box with infinite walls. The resulting perturbation equations have simple, analytic solutions. The procedure for normalization of the wavefunction corrections is demonstrated, and the perturbation energies and normalized wavefunctions are shown to approach the exact values. The method is applied to both the ground state and first excited state and can become a valuable component of a student’s introduction to perturbation analysis.
The authors propose a new method of solving the Schrodinger equation for a quantum system enclosed in a box with infinite potential walls. The method combines the variational technique with boundary perturbation theory and can be applied to a general non-separable case. When the Schrodinger equation for an enclosed system separates into an ordinary differential equation, the method gives the exact energy and wavefunction. As an application of the method the authors obtain the ground-state energy of the hydrogen atom placed off-centre in a spherical cavity. A generalisation of the variational boundary perturbation technique for finite potential walls is suggested.
Abstract As the first stage in a project aimed at finding exact bound-state solutions for the few-particle Schrödinger equation, some restricted two-and three- body systems are treated by Rayleigh–Schrödinger perturbation theory. Formal solutions for the perturbation equations are obtained by using standard techniques for solving differential equations. Particular attention is given to justifying the various boundary conditions, since the same conditions apply to formal solutions of the eigenvalue equations. It is shown that boundary conditions designed to preserve the Hermitian character of the Hamiltonian are sufficient to determine all parameters in the formal solutions. The procedure is demonstrated by application to a hydrogen atom perturbed by stationary point charges. Results are given for the ground and some excited states.
A perturbation theory is described which leads to two alternative methods for calculating the eigenvalues and normalized eigenstates of a perturbed Hamiltonian, the results being given to all orders in the perturbation. The expansions obtained are formulated in terms of two sets of partial sums which have simple, easily characterized forms, and they combine some of the advantages of both the Rayleigh-Schr\"odinger and Brillouin-Wigner perturbation methods while avoiding some of the difficulties of each. In particular, one form of the perturbation expansions given here will in most cases of interest have a larger radius of convergence than the Rayleigh-Schr\"odinger series. As is usual for infinite-order treatments, the explicit form of the final result applies only to nondegenerate levels. However, some of the intermediate relations obtained in the derivation are of general validity. Since certain classes of unlinked diagrams appear in the expansions, the method described here is not suitable for application to systems containing a large number of particles.