DOI: 10.1063/1.466883. Open-shell restricted Hartree–Fock perturbation theory: Some considerations and comparisons

Open-shell restricted Hartree–Fock perturbation theory: Some considerations and comparisons

10.1063/1.466883

Crossref journal-article

AIP Publishing

The Journal of Chemical Physics (317)

Abstract

A comparative study is presented of the various recently developed open-shell perturbation theories that are based on a restricted Hartree–Fock reference wave function. Included in this study are issues concerning spin contamination, implementational considerations, and numerical comparisons at the second-order of perturbation theory for equilibrium geometries, vibrational frequencies, and singlet–triplet energy differences. Based on all of these considerations, it is concluded that the z-averaged perturbation theory (ZAPT) method is to be preferred over the other recently devised spin–orbital perturbation theories, while the spin-free OPT2 method possesses some advantages and disadvantages relative to the ZAPT method. In particular, it is shown that OPT2 energies are not invariant to rotations among singly-occupied degenerate molecular orbitals.

Bibliography

Lee, T. J., Rendell, A. P., Dyall, K. G., & Jayatilaka, D. (1994). Open-shell restricted HartreeâFock perturbation theory: Some considerations and comparisons. The Journal of Chemical Physics, 100(10), 7400â7409.

Authors 4

Timothy J. Lee (first)
Alistair P. Rendell (additional)
Kenneth G. Dyall (additional)
Dylan Jayatilaka (additional)

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Dates

Type	When
Created	23 years, 1 month ago (July 26, 2002, 8:27 a.m.)
Deposited	1 year, 6 months ago (Feb. 6, 2024, 6:43 a.m.)
Indexed	1 month, 4 weeks ago (July 1, 2025, 9:06 a.m.)
Issued	31 years, 3 months ago (May 15, 1994)
Published	31 years, 3 months ago (May 15, 1994)
Published Print	31 years, 3 months ago (May 15, 1994)

Funders 0

None

BibTeX

@article{Lee_1994, title={Open-shell restricted Hartree–Fock perturbation theory: Some considerations and comparisons}, volume={100}, ISSN={1089-7690}, url={http://dx.doi.org/10.1063/1.466883}, DOI={10.1063/1.466883}, number={10}, journal={The Journal of Chemical Physics}, publisher={AIP Publishing}, author={Lee, Timothy J. and Rendell, Alistair P. and Dyall, Kenneth G. and Jayatilaka, Dylan}, year={1994}, month=may, pages={7400–7409} }

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