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Accurate and Efficient Perturbation Theory by Matrix Inversion

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B. Cameron Reed

Department of Physics, Alma College, Alma, MI 48801

J. Chem. Educ., 1999, 76 (10), p 1444

DOI: 10.1021/ed076p1444

Publication Date (Web): October 1, 1999

Abstract

A novel approach to time-independent perturbation theory is developed, which has significant advantages over the traditional Rayleigh-Schrödinger method. With this new method, energies and wave functions corresponding to perturbations of arbitrary strength acting on either degenerate or nondegenerate systems can be efficiently recovered in a conceptually straightforward matrix-inversion scheme. Tedious summations are eliminated, and no integrals beyond those appearing in first-order perturbation theory need be computed.