Singlet-triplet energy gaps in fluorine-substituted methylenes and silylenes

Seung Koo Shin; William A. Goddard; J. L. Beauchamp

doi:10.1063/1.458636

Singlet-triplet energy gaps in fluorine-substituted methylenes and silylenes

Seung Koo Shin
, William A. Goddard
, J. L. Beauchamp

California Institute of Technology

Research output: Contribution to journal › Article › peer-review

Abstract

We report singlet and triplet state splittings (ΔE_ST) 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 ΔE _ST for CH₂, CF₂, SiH₂, and SiF ₂ 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 ΔE_ST of CHF is 14.7±0.2 kcal/mol.

Original language	English
Pages (from-to)	4986-4993
Number of pages	8
Journal	Journal of Chemical Physics
Volume	93
Issue number	7
DOIs	https://doi.org/10.1063/1.458636
Publication status	Published - 1 Jan 1990
Externally published	Yes

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title = "Singlet-triplet energy gaps in fluorine-substituted methylenes and silylenes",

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 ΔE ST for CH2, CF2, SiH2, and SiF 2 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.",

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AU - Shin, Seung Koo

AU - Goddard, William A.

AU - Beauchamp, J. L.

PY - 1990/1/1

Y1 - 1990/1/1

N2 - 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 ΔE ST for CH2, CF2, SiH2, and SiF 2 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.

AB - 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 ΔE ST for CH2, CF2, SiH2, and SiF 2 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.

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DO - 10.1063/1.458636

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SP - 4986

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JO - Journal of Chemical Physics

JF - Journal of Chemical Physics

IS - 7

ER -

Singlet-triplet energy gaps in fluorine-substituted methylenes and silylenes

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