Coulomb Sturmians as a basis for molecular calculations

John Scales Avery; James Emil Avery

doi:10.1080/00268976.2012.658876

Coulomb Sturmians as a basis for molecular calculations

12 Citations (Scopus)

Abstract

Almost all modern quantum chemistry programs use Gaussian basis sets even though Gaussians cannot accurately represent the cusp at atomic nuclei, nor can they represent the slow decay of the wave function at large distances. The reason that Gaussians dominate quantum chemistry today is the great mathematical difficulty of evaluating interelectron repulsion integrals when exponential-type orbitals (ETOs) are used. In this paper we show that when many-centre Coulomb Sturmian ETOs are used as a basis, the most important integrals can be evaluated rapidly and accurately by means of the theory of hyperspherical harmonics. For the remaining many-centre integrals, Coulomb Sturmians are shown to have advantages over other ETOs. Pilot calculations are performed on N-electron molecules using the Generalized Sturmian Method.

Original language	English
Journal	Molecular Physics
Volume	110
Issue number	15-16
Pages (from-to)	1593-1608
Number of pages	16
ISSN	0026-8976
DOIs	https://doi.org/10.1080/00268976.2012.658876
Publication status	Published - 10 Aug 2012
Externally published	Yes

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title = "Coulomb Sturmians as a basis for molecular calculations",

abstract = "Almost all modern quantum chemistry programs use Gaussian basis sets even though Gaussians cannot accurately represent the cusp at atomic nuclei, nor can they represent the slow decay of the wave function at large distances. The reason that Gaussians dominate quantum chemistry today is the great mathematical difficulty of evaluating interelectron repulsion integrals when exponential-type orbitals (ETOs) are used. In this paper we show that when many-centre Coulomb Sturmian ETOs are used as a basis, the most important integrals can be evaluated rapidly and accurately by means of the theory of hyperspherical harmonics. For the remaining many-centre integrals, Coulomb Sturmians are shown to have advantages over other ETOs. Pilot calculations are performed on N-electron molecules using the Generalized Sturmian Method.",

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AU - Avery, John Scales

AU - Avery, James Emil

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N2 - Almost all modern quantum chemistry programs use Gaussian basis sets even though Gaussians cannot accurately represent the cusp at atomic nuclei, nor can they represent the slow decay of the wave function at large distances. The reason that Gaussians dominate quantum chemistry today is the great mathematical difficulty of evaluating interelectron repulsion integrals when exponential-type orbitals (ETOs) are used. In this paper we show that when many-centre Coulomb Sturmian ETOs are used as a basis, the most important integrals can be evaluated rapidly and accurately by means of the theory of hyperspherical harmonics. For the remaining many-centre integrals, Coulomb Sturmians are shown to have advantages over other ETOs. Pilot calculations are performed on N-electron molecules using the Generalized Sturmian Method.

AB - Almost all modern quantum chemistry programs use Gaussian basis sets even though Gaussians cannot accurately represent the cusp at atomic nuclei, nor can they represent the slow decay of the wave function at large distances. The reason that Gaussians dominate quantum chemistry today is the great mathematical difficulty of evaluating interelectron repulsion integrals when exponential-type orbitals (ETOs) are used. In this paper we show that when many-centre Coulomb Sturmian ETOs are used as a basis, the most important integrals can be evaluated rapidly and accurately by means of the theory of hyperspherical harmonics. For the remaining many-centre integrals, Coulomb Sturmians are shown to have advantages over other ETOs. Pilot calculations are performed on N-electron molecules using the Generalized Sturmian Method.

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DO - 10.1080/00268976.2012.658876

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JO - Molecular Physics

JF - Molecular Physics

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ER -

Coulomb Sturmians as a basis for molecular calculations

Abstract

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