Computational study on the kinetics and mechanisms for the reactions of HCO with HONO and HNOH

Z. F. Xu, Ming-Chang Lin*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

9 Scopus citations

Abstract

The kinetics and mechanisms of the HCO reactions with HONO and HNOH have been studied at the G2M level of theory based on the geometric parameters optimized at BH&HLYP/6-311G(d,p). The rate constants in the temperature range 200-3000 K at different pressures have been predicted by microcanonical RRKM and/or variational transition state theory calculations with Eckart tunneling corrections. For the HCO + HONO reaction, hydrogen abstraction from trans-HONO and cis-HONO by HCO produces H2CO + NO2, with the latter being dominant. Two other channels involving cis-HONO by the association/decomposition mechanism via the HC(O)N(O)OH intermediate, which could fragment to give H2O + CO + NO at high temperatures, were also found to be important. For the HCO + HNOH reaction, three reaction channels were identified: one association reaction giving a stable intermediate, HC(O)N(H)OH (LM2), and two hydrogen abstraction channels producing H2CO and H2NOH. The dominant products were predicted to be the formation of LM2 at low temperatures and H2NOH + CO at middle and high temperatures.

Original languageEnglish
Pages (from-to)178-187
Number of pages10
JournalInternational Journal of Chemical Kinetics
Volume36
Issue number3
DOIs
StatePublished - 1 Jan 2004

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