Efficient algorithm for two-center Coulomb and exchange integrals of electronic prolate spheroidal orbitals

DOI10.1016/J.JCP.2012.04.022zbMATH Open1253.81054DBLPjournals/jcphy/Mendl12arXiv1203.6256OpenAlexW1969970971WikidataQ59793030 ScholiaQ59793030MaRDI QIDQ450197FDOQ450197

Authors: Christian B. Mendl 

Publication date: 13 September 2012

Published in: Journal of Computational Physics (Search for Journal in Brave)

Abstract: We present a fast algorithm to calculate Coulomb/exchange integrals of prolate spheroidal electronic orbitals, which are the exact solutions of the single-electron, two-center Schr"odinger equation for diatomic molecules. Our approach employs Neumann's expansion of the Coulomb repulsion 1/|x-y|, solves the resulting integrals symbolically in closed form and subsequently performs a numeric Taylor expansion for efficiency. Thanks to the general form of the integrals, the obtained coefficients are independent of the particular wavefunctions and can thus be reused later. Key features of our algorithm include complete avoidance of numeric integration, drafting of the individual steps as fast matrix operations and high accuracy due to the exponential convergence of the expansions. Application to the diatomic molecules O2 and CO exemplifies the developed methods, which can be relevant for a quantitative understanding of chemical bonds in general.

Full work available at URL: https://arxiv.org/abs/1203.6256

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zbMATH Keywords

diatomic moleculesLaguerre expansionsCoulomb integralsmolecular orbitalsprolate spheroidal coordinatesSchrödinger equation

Mathematics Subject Classification ID

Orthogonal polynomials and functions of hypergeometric type (Jacobi, Laguerre, Hermite, Askey scheme, etc.) (33C45) Computational methods for problems pertaining to quantum theory (81-08) Closed and approximate solutions to the Schrödinger, Dirac, Klein-Gordon and other equations of quantum mechanics (81Q05) Selfadjoint operator theory in quantum theory, including spectral analysis (81Q10) Molecular physics (81V55)

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Cited In (2)

• Fast computation of close-coupling exchange integrals using polynomials in a tree representation
• Two-center overlap integrals, three dimensional adaptive integration, and prolate ellipsoidal coordinates

Uses Software

• FermiFab

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