Author:
Troe Jürgen,Ushakov Vladimir G.
Abstract
Abstract
Expressions for representing the pressure dependence of unimolecular
dissociation and the reverse recombination reactions are
compared. Situations are considered where the broadening of the
corresponding falloff curves is particularly pronounced, i.e. where
broadening factors at the center of the falloff curves,
F
cent, are very small and falloff curves correspondingly
become very “broad”. Such situations arise when unimolecular
reactions of molecules with large numbers of low-frequency modes and
high-temperature situations are considered. Recombination reactions of
polyatomic species in atmospheric chemistry and dissociation reactions
of large molecules in combustion are the fields of application of the
present results. While previously proposed expressions for asymmetric
broadening factors showed artifacts when F
cent decreased
to values below about 0.4, alternative functions are described which
avoid these problems for situations where F
cent decreases
to values far below 0.1.
Subject
Physical and Theoretical Chemistry
Cited by
55 articles.
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