A computational study of the kinetics and mechanism for the reaction of HCO with HNO
Abstract
The mechanism for the reaction of HCO with HNO has been studied at the G2M level of theory, based on the geometric parameters optimized by the BH&HLYP/6‐311G(d, p) method. There are three direct hydrogen abstraction channels producing (1) H2CO + NO, (2) H2NO + CO, and (3) HNOH + CO with barriers of 3.7, 3.9, and 10.4 kcal/mol, respectively. Another important reaction channel, (4), involves an association process forming HN(O)CHO (LM1) with a very small barrier and the subsequent isomerization and decomposition of LM1 producing HNOH + CO as major products. The rate constants of the dominant reaction channels (1), (2), and (4) in the temperature range 200–3000 K have been predicted by the microcanonical RRKM and transition state theory calculations with Eckart tunneling corrections. The theoretical result shows that in the high temperature range ( T > 1500 K), k1 (H2CO + NO) and k2(H2NO + CO) are preponderant, while in the low temperature range, both k4(LM1) and k4(HNOH + CO) appear to be dominant at high and low pressures, respectively. © 2004 Wiley Periodicals, Inc. Int J Chem Kinet 36: 205–215, 2004
Document Details
- Document Type
- Pub Defense Publication
- Publication Date
- Feb 04, 2004
- Source ID
- 10.1002/kin.10178
Entities
People
- Ming‐Fong Lin
- Z. F. Xu
Organizations
- Office of Naval Research