Theory of Thermal Unimolecular Reactions in the Fall‐off Range. II. Weak Collision Rate Constants

Wiley - Tập 87 Số 2 - Trang 169-177 - 1983
Robert G. Gilbert1,2, K. Luther2, J. Troe2
1Department of Theoretical Chemistry, University of Sydney, N.S.W. 2006, Australia
2Institut für Physikalische Chemie der Universität Göttingen, Tammannstraße 6, D-3400 Göttingen, Germany

Tóm tắt

AbstractThe master equation of thermal unimolecular reactions in the fall‐off range has been solved for a number of representative molecular systems. Weak collision broadening factors FWC(k0/k∞) are derived and represented empirically. Weak collision efficiencies βc for the low pressure range are calculated for very high temperatures. Combined with earlier representations (part I) of strong collision broadening factors FSC(k0/k∞), compact empirical expressions for the rate coefficient in the full fall‐off range are proposed. These expressions are useful for data representation and modeling of complex reaction systems which involve isomerization, dissociation and recombination reactions.

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Wiley

Tập 87 Số 2

169-177

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