標題: Kinetics and Mechanism of the NCN+NO2 Reaction Studied by Experiment and Theory
作者: Yang, Tsung-Ju
Wang, Niann S.
Lee, L. C.
Xu, Z. F.
Lin, M. C.
應用化學系
應用化學系分子科學碩博班
Department of Applied Chemistry
Institute of Molecular science
公開日期: 16-Oct-2008
摘要: The rate constant for the NCN + NO2 reaction has been measured by a laser photolysis/laser-induced fluorescence technique in the temperature range of 260-296 K at pressures between 100 and 500 Torr with He and N-2 as buffer gases. The NCN radical was produced from the photolysis of NCN3 at 193 nm and monitored by laser-induced fluorescence with a dye laser at 329.01 nm. The rate constant was found to increase with pressure but decrease with temperature, indicating that the reaction occurs via a long-lived intermediate stabilized by collisions with buffer gas. The reaction mechanism and rate constant are also theoretically predicted for the temperature range of 200-2000 K and the He and N-2 pressure range of 10(-4) Torr to 1000 atm based on dual-channel Rice-Ramsperger-Kassel-Marcus (RRKM) theory with the potential energy surface evaluated at the G2M//B3LYP/6-311+G(d) level. In the low-temperature range (< 700 K), the most favorable reaction is the barrierless association channel that leads to the intermediate complex (NCN-NO2). At high temperature, the direct O-abstraction reaction with a barrier of 9.8 kcal/mol becomes the dominant channel. The rate constant calculated by RRKM theory agrees reasonably well with experimental data.
URI: http://dx.doi.org/10.1021/jp805311u
http://hdl.handle.net/11536/8243
ISSN: 1089-5639
DOI: 10.1021/jp805311u
期刊: JOURNAL OF PHYSICAL CHEMISTRY A
Volume: 112
Issue: 41
起始頁: 10185
結束頁: 10192
Appears in Collections:Articles


Files in This Item:

  1. 000259943100015.pdf