DOI: 10.1063/1.446452. Electronic symmetry breaking in polyatomic molecules. Multiconfiguration self-consistent field study of the cyclopropenyl radical C3H3

Electronic symmetry breaking in polyatomic molecules. Multiconfiguration self-consistent field study of the cyclopropenyl radical C3H3

10.1063/1.446452

Crossref journal-article

AIP Publishing

The Journal of Chemical Physics (317)

Abstract

For equilateral triangle geometries (point group D3h), the C3H3 radical has a degenerate 2E″ electronic ground state. Although the 2A2 and 2B1 components separate in energy for C2v geometries, these two components should have identical energies for equilateral triangle structures. In fact, when approximate wave functions are used and the orbitals not required to transform according to the D3h irreducible representations, an energy separation between the 2A2 and 2B1 components is observed. At the single configuration self-consistent field (SCF) level of theory this separation is 2.8 kcal with a double-zeta basis set and 2.4 kcal with double-zeta plus polarization. It has been demonstrated that this spurious separation may be greatly reduced using multiconfiguration self-consistent field (up to 7474 variationally optimum configurations) and configuration interaction (up to 60 685 space and spin adapted configurations) techniques. Configurations differing by three and four electrons from the Hartree–Fock reference function are found necessary to reduce the 2A2-2B1 separation to below 0.5 kcal.

Bibliography

Hoffmann, M. R., Laidig, W. D., Kim, K. S., Fox, D. J., & Schaefer, H. F. (1984). Electronic symmetry breaking in polyatomic molecules. Multiconfiguration self-consistent field study of the cyclopropenyl radical C3H3. The Journal of Chemical Physics, 80(1), 338â343.

Authors 5

Mark R. Hoffmann (first)
William D. Laidig (additional)
Kwang S. Kim (additional)
Douglas J. Fox (additional)
Henry F. Schaefer (additional)

References 27 Referenced 20

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10.1016/0022-2860(73)80002-X / J. Mol. Struct. (1973)
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Dates

Type	When
Created	22 years, 6 months ago (Feb. 28, 2003, 12:18 p.m.)
Deposited	1 year, 6 months ago (Feb. 9, 2024, 8:38 p.m.)
Indexed	2 days, 8 hours ago (Sept. 3, 2025, 6:35 a.m.)
Issued	41 years, 8 months ago (Jan. 1, 1984)
Published	41 years, 8 months ago (Jan. 1, 1984)
Published Print	41 years, 8 months ago (Jan. 1, 1984)

Funders 0

None

BibTeX

@article{Hoffmann_1984, title={Electronic symmetry breaking in polyatomic molecules. Multiconfiguration self-consistent field study of the cyclopropenyl radical C3H3}, volume={80}, ISSN={1089-7690}, url={http://dx.doi.org/10.1063/1.446452}, DOI={10.1063/1.446452}, number={1}, journal={The Journal of Chemical Physics}, publisher={AIP Publishing}, author={Hoffmann, Mark R. and Laidig, William D. and Kim, Kwang S. and Fox, Douglas J. and Schaefer, Henry F.}, year={1984}, month=jan, pages={338–343} }

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