Coulomb Sturmians as a basis for molecular calculations
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Coulomb Sturmians as a basis for molecular calculations. / Avery, John Scales; Avery, James Emil.
In: Molecular Physics, Vol. 110, No. 15-16, 2012, p. 1593-1608.Research output: Contribution to journal › Journal article › Research › peer-review
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TY - JOUR
T1 - Coulomb Sturmians as a basis for molecular calculations
AU - Avery, John Scales
AU - Avery, James Emil
PY - 2012
Y1 - 2012
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
VL - 110
SP - 1593
EP - 1608
JO - Molecular Physics
JF - Molecular Physics
SN - 0026-8976
IS - 15-16
ER -
ID: 46460422