Relationship between mode specific and thermal unimolecular rate constants for HOCL → OH + Cl dissociation

Kihyung Song, Lipeng Sun, William L. Hase, S. Yu Grebenshchikov, Reinhard Schinke

Research output: Contribution to journalArticle

12 Scopus citations

Abstract

Recent quantum dynamical calculations [Hauschildt, J.; et al. Chem. Phys. Lett. 1999, 300, 569] have shown that HOCl → OH + Cl dissociation on the ground-state potential energy surface, and for J = 0, occurs predominantly via isolated compound-state resonances, whose rates are highly mode-specific. In this work, these resonance rates are averaged to calculate the HOCl → OH + Cl unimolecular rate constant as a function of temperature and pressure. The result is compared with the standard pressure and temperature dependent RRKM unimolecular rate constant. It is found that the state-specificity makes the pressure-dependent rates significantly lower than the RRKM rates in the intermediate pressure regime.

Original languageEnglish
Pages (from-to)8339-8344
Number of pages6
JournalJournal of Physical Chemistry A
Volume106
Issue number36
DOIs
StatePublished - Sep 12 2002

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