Abstract
The relative abilities of Hartree-Fock, density-functional theory (DFT) and coupled-cluster theory were used to investigate symmetry breaking in polyatomic molecules. It was observed that for degenerate electronic states, symmetry breaking in the nuclear framework may result from first-order Jahn-Teller (SOJT) effects. Displacements along Non totally symmetric nuclear coordinates, however, may lead to mixing of the states if their respective irreducible representations correlate in the reduced symmetry point group. Coupled-cluster theory correctly describes the strength of SOJT coupling, assuming that the full CCSDT method provides a reasonable approximation of the exact wave function.
Recommended Citation
N. J. Russ et al., "Real Versus Artifactual Symmetry-Breaking Effects in Hartree-Fock, Density-Functional, and Coupled-Cluster Methods," Journal of Chemical Physics, vol. 120, no. 16, pp. 7298 - 7306, American Institute of Physics, Apr 2004.
The definitive version is available at https://doi.org/10.1063/1.1687336
Department(s)
Chemistry
Publication Status
Available Access
International Standard Serial Number (ISSN)
0021-9606
Document Type
Article - Journal
Document Version
Final Version
File Type
text
Language(s)
English
Rights
© 2024 American Institute of Physics, All rights reserved.
Publication Date
22 Apr 2004
