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 Citationer (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.

Originalsprog	Engelsk
Tidsskrift	Molecular Physics
Vol/bind	110
Udgave nummer	15-16
Sider (fra-til)	1593-1608
Antal sider	16
ISSN	0026-8976
DOI	https://doi.org/10.1080/00268976.2012.658876
Status	Udgivet - 10 aug. 2012
Udgivet eksternt	Ja

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10.1080/00268976.2012.658876

Citationsformater

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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.",

author = "Avery, {John Scales} and Avery, {James Emil}",

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doi = "10.1080/00268976.2012.658876",

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T1 - Coulomb Sturmians as a basis for molecular calculations

AU - Avery, John Scales

AU - Avery, James Emil

PY - 2012/8/10

Y1 - 2012/8/10

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.

U2 - 10.1080/00268976.2012.658876

DO - 10.1080/00268976.2012.658876

M3 - Journal article

SN - 0026-8976

VL - 110

SP - 1593

EP - 1608

JO - Molecular Physics

JF - Molecular Physics

IS - 15-16

ER -

Coulomb Sturmians as a basis for molecular calculations

Abstract

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