Ab initio reaction pathways for photodissociation and isomerization of nitromethane on four singlet potential energy surfaces with three roaming paths

Miho Isegawa, Fengyi Liu, Satoshi Maeda, Keiji Morokuma

研究成果: Contribution to journalArticle査読

20 被引用数 (Scopus)

抄録

Photodissociation pathways of nitromethane following π → π electronic excitation are reported. The potential energy surfaces for four lowest singlet states are explored, and structures of many intermediates, dissociation limits, transition states, and minimum energy conical intersections were determined using the automated searching algorism called the global reaction route mapping strategy. Geometries are finally optimized at CASSCF(14e,11o) level and energies are computed at CAS(14o,11e)PT2 level. The calculated preferable pathways and important products qualitatively explain experimental observations. The major photodissociation product CH3 and NO2 (2B2) is formed by direct dissociation from the S1 state. Important pathways involving S1 and S0 states for production of various dissociation products CH 3NO + O (1D), CH3O(X2E) + NO (X 2Π ), CH2NO + OH, and CH2O + HNO, as well as various isomerization pathways have been identified. Three roaming processes also have been identified: the O atom roaming in O dissociation from CH 3NO2, the OH radical roaming in OH dissociation from CH2N(O)(OH), and the NO roaming in NO dissociation from CH 3ONO.

本文言語英語
論文番号244310
ジャーナルJournal of Chemical Physics
140
24
DOI
出版ステータス出版済み - 1 1 2014
外部発表はい

All Science Journal Classification (ASJC) codes

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

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