Dissociation dynamics of FCO and HCO radicals

J. S. Francisco; A. N. Goldstein; I. H. Williams

doi:10.1063/1.454959

Dissociation dynamics of FCO and HCO radicals

J. S. Francisco, A. N. Goldstein, I. H. Williams

Department of Chemistry

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Abstract

Dissociation energies and barriers to dissociation for XCO→X + CO have been calculated for X̃²A′ and Ã ²π states of FCO and HCO by ab initio molecular orbital methods. At the PUMP4//UMP2/6-311G* level, D₂₉₈° (F-CO) = 22.3 kcal mol^-1 and ΛH₂₉₈ = 24.2 kcal mol^-1 for dissociation of ground-state FCO; these values are much higher than the corresponding bond energy and activation enthalpy for HCO dissociation. Calculated RRKM rate constants suggests that the lifetime of FCO under stratospheric conditions is sufficient to allow bimolecular reactions to compete with dissociation. Reaction with O₂ may provide an in situ source of stratospheric CO₂.

Original language	English
Pages (from-to)	3044-3049
Number of pages	6
Journal	The Journal of Chemical Physics
Volume	89
Issue number	5
DOIs	https://doi.org/10.1063/1.454959
Publication status	Published - 1 Jan 1988

ASJC Scopus subject areas

General Physics and Astronomy
Physical and Theoretical Chemistry

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title = "Dissociation dynamics of FCO and HCO radicals",

abstract = "Dissociation energies and barriers to dissociation for XCO→X + CO have been calculated for {\~X}2A′ and {\~A} 2π states of FCO and HCO by ab initio molecular orbital methods. At the PUMP4//UMP2/6-311G* level, D298° (F-CO) = 22.3 kcal mol-1 and ΛH298 = 24.2 kcal mol-1 for dissociation of ground-state FCO; these values are much higher than the corresponding bond energy and activation enthalpy for HCO dissociation. Calculated RRKM rate constants suggests that the lifetime of FCO under stratospheric conditions is sufficient to allow bimolecular reactions to compete with dissociation. Reaction with O2 may provide an in situ source of stratospheric CO2.",

author = "Francisco, {J. S.} and Goldstein, {A. N.} and Williams, {I. H.}",

year = "1988",

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T1 - Dissociation dynamics of FCO and HCO radicals

AU - Francisco, J. S.

AU - Goldstein, A. N.

AU - Williams, I. H.

PY - 1988/1/1

Y1 - 1988/1/1

N2 - Dissociation energies and barriers to dissociation for XCO→X + CO have been calculated for X̃2A′ and Ã 2π states of FCO and HCO by ab initio molecular orbital methods. At the PUMP4//UMP2/6-311G* level, D298° (F-CO) = 22.3 kcal mol-1 and ΛH298 = 24.2 kcal mol-1 for dissociation of ground-state FCO; these values are much higher than the corresponding bond energy and activation enthalpy for HCO dissociation. Calculated RRKM rate constants suggests that the lifetime of FCO under stratospheric conditions is sufficient to allow bimolecular reactions to compete with dissociation. Reaction with O2 may provide an in situ source of stratospheric CO2.

AB - Dissociation energies and barriers to dissociation for XCO→X + CO have been calculated for X̃2A′ and Ã 2π states of FCO and HCO by ab initio molecular orbital methods. At the PUMP4//UMP2/6-311G* level, D298° (F-CO) = 22.3 kcal mol-1 and ΛH298 = 24.2 kcal mol-1 for dissociation of ground-state FCO; these values are much higher than the corresponding bond energy and activation enthalpy for HCO dissociation. Calculated RRKM rate constants suggests that the lifetime of FCO under stratospheric conditions is sufficient to allow bimolecular reactions to compete with dissociation. Reaction with O2 may provide an in situ source of stratospheric CO2.

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Dissociation dynamics of FCO and HCO radicals

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