Ab initio MO and TST calculations for the rate constant of the HNO + NO2 → HONO + NO reaction Article

Mebel, AM, Lin, MC, Morokuma, K. (1998). Ab initio MO and TST calculations for the rate constant of the HNO + NO2 → HONO + NO reaction . INTERNATIONAL JOURNAL OF CHEMICAL KINETICS, 30(10), 729-736. 10.1002/(SICI)1097-4601(1998)30:10<729::AID-KIN5>3.0.CO;2-X

cited authors

  • Mebel, AM; Lin, MC; Morokuma, K

authors

abstract

  • Potential-energy surfaces for various channels of the HNO + NO2 reaction have been studied at the G2M(RCC,MP2) level, The calculations show that direct hydrogen abstraction leading to the NO + cis-HONO products should be the most significant reaction mechanism. Based on TST calculations of the rate constant, this channel is predicted to have an activation energy of 6-7 kcal/mol and an A factor of ca. 10-11 cm3 molecule-1 s-1 at ambient temperature, Direct H-abstraction giving NO + trans-HONO has a high barrier on PES and the formation of trans-HONO would rather occur by the addition/1,3-H shift mechanism via the HN(O)NO2 intermediate or by the secondary isomerization of cis-HONO. The formation of NO + HNO2 can take place by direct hydrogen transfer with the barrier of ca, 3 kcal/mol higher than that for the NO + cis-HONO channel. The formation of HNO2 by oxygen abstraction is predicted to be the least significant reaction channel. The rate constant calculated in the temperature range 300-5000 K for the lowest energy path producing NO + cis-HONO gave rise to ka = 7.34 · 10-20T2 64exp(-2034/T) cm3 molecule-1 S-1. © 1998 John Wiley & Sons, Inc.

publication date

  • January 1, 1998

published in

start page

  • 729

end page

  • 736

volume

  • 30

issue

  • 10