標題: A novel mechanism for the isomerization of N2O4 and its implication for the reaction with H2O and acid rain formation
作者: Putikam, Raghunath
Lin, Ming-Chang
應用化學系分子科學碩博班
Institute of Molecular science
關鍵字: HONO and HNO3 formation;N2O4 hydrolysis;N2O4 isomerization and reaction;roaming-like transition state
公開日期: 15-Jun-2018
摘要: We have discovered, by high-level quantum-chemical calculations, a new and predominant isomerization mechanism for N2O4 -> ONONO2 via a roaming-like transition state occurring unimolecularly or bimolecularly during collision with H2O. The new mechanism allows N2O4 to react with H2O with a significantly lower barrier (< 13.1 kcal/mol) than the commonly known tight transition state (similar to 30-45 kcal/mol) by concurrent stretching of the N-N bond and rotation of one of the NO2 groups to form trans-ONONO2, which then undergoes a rapid metathetical reaction with H2O in the gas phase and in aqueous solution. The results have a significant implication for the hydrolysis of N2O4 in water to produce HONO and HNO3. Rate constants for the isomerization and hydrolysis reactions have been predicted for atmospheric modeling applications.
URI: http://dx.doi.org/10.1002/qua.25560
http://hdl.handle.net/11536/144978
ISSN: 0020-7608
DOI: 10.1002/qua.25560
期刊: INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY
Volume: 118
Appears in Collections:Articles