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

doi:10.1021/jp014689l

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

Chemistry and Biochemistry

Research output: Contribution to journal › Article

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 language	English
Pages (from-to)	8339-8344
Number of pages	6
Journal	Journal of Physical Chemistry A
Volume	106
Issue number	36
DOIs	https://doi.org/10.1021/jp014689l
State	Published - Sep 12 2002

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Song, K., Sun, L., Hase, W. L., Grebenshchikov, S. Y., & Schinke, R. (2002). Relationship between mode specific and thermal unimolecular rate constants for HOCL → OH + Cl dissociation. Journal of Physical Chemistry A, 106(36), 8339-8344. https://doi.org/10.1021/jp014689l

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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.",

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AU - Song, Kihyung

AU - Sun, Lipeng

AU - Hase, William L.

AU - Grebenshchikov, S. Yu

AU - Schinke, Reinhard

PY - 2002/9/12

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AB - 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.

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