Relationship between mode specific and thermal unimolecular rate constants for 
HOCl -> OH+Cl dissociation

Song, K. H.; Sun, L. P.; Hase, W. L.; Grebenshchikov, S. Y.; Schinke, R.

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Relationship between mode specific and thermal unimolecular rate constants for HOCl -> OH+Cl dissociation

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Grebenshchikov, S. Y.
Max Planck Institute for Dynamics and Self-Organization, Max Planck Society;

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Schinke, R.
Max Planck Institute for Dynamics and Self-Organization, Max Planck Society;

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Citation

Song, K. H., Sun, L. P., 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.

Cite as: https://hdl.handle.net/11858/00-001M-0000-0029-175B-D

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.