Contrasting origins of the isomerization barriers for vinylidene, fluorovinylidene, and difluorovinylidene

Zhi Heng Loh; Robert W. Field

doi:10.1063/1.1540625

Contrasting origins of the isomerization barriers for vinylidene, fluorovinylidene, and difluorovinylidene

Zhi Heng Loh, Robert W. Field^*

^*Corresponding author for this work

Massachusetts Institute of Technology

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

23 Citations (Scopus)

Abstract

The origins of the isomerization barriers for H₂C=C, HFC=C, and F₂C=C were examined by employing a combination of quadratic configuration interaction and density functional theory calculations. It was found that the transition states involved in the isomerization of HFC=C via fluorine atom and hydrogen atom migration bear qualitatively similar bonding features to those observed in the case of TS_F and TS_H, thus providing support for the origins of the isomerization barriers for F₂C=C and H₂C=C. The violation of Hammond's postulate in the isomerization of H₂C=C was explained in terms of the strong covalent binding of the migrating hydrogen to the C=C bond observed in the AIM molecular graph of TS_H.

Original language	English
Pages (from-to)	4037-4044
Number of pages	8
Journal	Journal of Chemical Physics
Volume	118
Issue number	9
DOIs	https://doi.org/10.1063/1.1540625
Publication status	Published - Mar 1 2003
Externally published	Yes

ASJC Scopus Subject Areas

General Physics and Astronomy
Physical and Theoretical Chemistry

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abstract = "The origins of the isomerization barriers for H2C=C, HFC=C, and F2C=C were examined by employing a combination of quadratic configuration interaction and density functional theory calculations. It was found that the transition states involved in the isomerization of HFC=C via fluorine atom and hydrogen atom migration bear qualitatively similar bonding features to those observed in the case of TSF and TSH, thus providing support for the origins of the isomerization barriers for F2C=C and H2C=C. The violation of Hammond's postulate in the isomerization of H2C=C was explained in terms of the strong covalent binding of the migrating hydrogen to the C=C bond observed in the AIM molecular graph of TSH.",

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N2 - The origins of the isomerization barriers for H2C=C, HFC=C, and F2C=C were examined by employing a combination of quadratic configuration interaction and density functional theory calculations. It was found that the transition states involved in the isomerization of HFC=C via fluorine atom and hydrogen atom migration bear qualitatively similar bonding features to those observed in the case of TSF and TSH, thus providing support for the origins of the isomerization barriers for F2C=C and H2C=C. The violation of Hammond's postulate in the isomerization of H2C=C was explained in terms of the strong covalent binding of the migrating hydrogen to the C=C bond observed in the AIM molecular graph of TSH.

AB - The origins of the isomerization barriers for H2C=C, HFC=C, and F2C=C were examined by employing a combination of quadratic configuration interaction and density functional theory calculations. It was found that the transition states involved in the isomerization of HFC=C via fluorine atom and hydrogen atom migration bear qualitatively similar bonding features to those observed in the case of TSF and TSH, thus providing support for the origins of the isomerization barriers for F2C=C and H2C=C. The violation of Hammond's postulate in the isomerization of H2C=C was explained in terms of the strong covalent binding of the migrating hydrogen to the C=C bond observed in the AIM molecular graph of TSH.

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Contrasting origins of the isomerization barriers for vinylidene, fluorovinylidene, and difluorovinylidene

Abstract

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