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

Kihyung Song; William L. Hase

doi:10.1021/jp972581t

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

Kihyung Song, William L. Hase

Chemistry and Biochemistry

Research output: Contribution to journal › Article › peer-review

13 Scopus citations

Abstract

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(ω, E) and the Lindemann-Hinshelwood thermal rate constant k_uni(ω, 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(ω, E) and k_uni(ω, T).

Original language	English
Pages (from-to)	1292-1296
Number of pages	5
Journal	Journal of Physical Chemistry A
Volume	102
Issue number	8
DOIs	https://doi.org/10.1021/jp972581t
State	Published - Feb 19 1998

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abstract = "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 PE(k) distribution. In the work presented here, this PE(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(ω, E) and the Lindemann-Hinshelwood thermal rate constant kuni(ω, 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(ω, E) and kuni(ω, T).",

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AU - Song, Kihyung

AU - Hase, William L.

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Y1 - 1998/2/19

N2 - 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 PE(k) distribution. In the work presented here, this PE(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(ω, E) and the Lindemann-Hinshelwood thermal rate constant kuni(ω, 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(ω, E) and kuni(ω, T).

AB - 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 PE(k) distribution. In the work presented here, this PE(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(ω, E) and the Lindemann-Hinshelwood thermal rate constant kuni(ω, 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(ω, E) and kuni(ω, T).

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JO - Journal of Physical Chemistry A

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ER -

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

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