Role of state specificity in the temperature- and pressure-dependent unimolecular rate constants for HO2→H+O2 dissociation

被引：10

作者：

Song, K

Hase, WL ^{[1
]}

机构：

[1] Wayne State Univ, Dept Chem, Detroit, MI 48202 USA

[2] Korea Natl Univ Educ, Dept Chem, Chungbuk 363791, South Korea

来源：

JOURNAL OF PHYSICAL CHEMISTRY A | 1998年 / 102卷 / 08期

关键词：

D O I：

10.1021/jp972581t

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

Recent quantum dynamical calculations have shown that HO2 dissociates via isolated resonances, which have a distribution of rate constants that is statistical state-specific and well-described by the Porter-Thomas P-E(k) distribution. In the work presented here, this P-E(k) distribution is incorporated into RRKM theory to see how statistical fluctuations in state-specific rate constants affect the collision-averaged chemical activation rate constant k(omega, E) and the Lindemann-Hinshelwood thermal rate constant k(uni)(omega, T) for HO2 dissociation. Both active and adiabatic treatments are considered for the K quantum number. The calculations suggest the effect of statistical state specificity should be detectable in measurements of k(omega, E) and k(uni)(omega, T).

引用

页码：1292 / 1296

页数：5

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