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A general formula for Rayleigh-Schroedinger perturbation energy utilizing a power series expansion of the quantum mechanical Hamiltonian
Author(s) -
John M. Herbert
Publication year - 1997
Language(s) - English
Resource type - Reports
DOI - 10.2172/453740
Subject(s) - hamiltonian (control theory) , power series , perturbation (astronomy) , schrödinger's cat , quantum , schrödinger equation , hamiltonian system , mathematics , mathematical physics , energy operator , physics , classical mechanics , quantum mechanics , mathematical analysis , energy (signal processing) , mathematical optimization
Perturbation theory has long been utilized by quantum chemists as a method for approximating solutions to the Schroedinger equation. Perturbation treatments represent a system`s energy as a power series in which each additional term further corrects the total energy; it is therefore convenient to have an explicit formula for the nth-order energy correction term. If all perturbations are collected into a single Hamiltonian operator, such a closed-form expression for the nth-order energy correction is well known; however, use of a single perturbed Hamiltonian often leads to divergent energy series, while superior convergence behavior is obtained by expanding the perturbed Hamiltonian in a power series. This report presents a closed-form expression for the nth-order energy correction obtained using Rayleigh-Schroedinger perturbation theory and a power series expansion of the Hamiltonian

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