Singlet–triplet energy gaps in fluorine-substituted methylenes and silylenes
- 1 October 1990
- journal article
- conference paper
- Published by AIP Publishing in The Journal of Chemical Physics
- Vol. 93 (7) , 4986-4993
- https://doi.org/10.1063/1.458636
Abstract
We report singlet and triplet state splittings (ΔEST) for fluorine‐substituted methylenes and silylenes using dissociation‐consistent configuration interaction (CI) (based on generalized valence bond wave functions). These relatively simple CI calculations emphasize correlation consistency between the singlet and triplet states. Values of ΔEST for CH2, CF2, SiH2, and SiF2 are in excellent agreement with available experimental results, and we expect the predictions for the other cases CHF (14.5) and SiHF (41.3) to be equally accurate. This result strongly suggests that the correct choice among the experimental values for ΔEST of CHF is 14.7±0.2 kcal/mol.Keywords
This publication has 28 references indexed in Scilit:
- The carbon-carbon double bond of tetrafluoroethyleneJournal of the American Chemical Society, 1988
- Geometrical structures, force constants, and vibrational spectra of SiH, SiH2, SiH3, and SiH4Chemical Physics, 1986
- The potential surface of X̃ 3B1 methylene (CH2) and the singlet–triplet splittingThe Journal of Chemical Physics, 1986
- Halocarbenes CHF, CHCl, and CHBr: geometries, singlet-triplet separations, and vibrational frequenciesJournal of the American Chemical Society, 1986
- Singlet-triplet splittings in CF3-substituted carbenesThe Journal of Physical Chemistry, 1986
- Structural and energetic features of fully substituted silylenes, disilenes, and silylsilylenes (SiX2, X2SiSiX2, and XSiSiX3; X = lithium, methyl, and fluorine)Journal of the American Chemical Society, 1985
- Methylsilylene, silaethylene, and silylmethylene: energies, structures, and unimolecular reactivitiesJournal of the American Chemical Society, 1980
- The multiplicity of substituted acyclic carbenes and related moleculesJournal of the American Chemical Society, 1979
- Structure and energetics of simple carbenes methylene, fluoromethylene, chloromethylene, bromomethylene, difluoromethylene, and dichloromethyleneJournal of the American Chemical Society, 1977
- Generalized valence bond description of bonding in low-lying states of moleculesAccounts of Chemical Research, 1973