Photoinduced Nonadiabatic Decay and Dissociation Dynamics of Dimethylnitramine

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• 作者：Xuhui Zhuang ; Jun Wang ; Zhenggang Lan
• 刊名：The Journal of Physical Chemistry A
• 出版年：2013
• 出版时间：June 13, 2013
• 年：2013
• 卷：117
• 期：23
• 页码：4785-4793
• 全文大小：473K
• 年卷期：v.117,no.23(June 13, 2013)
• ISSN：1520-5215

文摘

Dimethylnitramine (DMNA) is a prototype system used in the investigation of the unimolecular decomposition mechanism of the nitramine-compound family. The photoinduced excited-state nonadiabatic processes and successive unimolecular dissociation of DMNA were investigated by trajectory surface-hopping dynamics at the semiempirical OM2/MRCI level. Two S₁/S₀ conical intersections (CI_01伪 and CI_01尾) were found to play essential roles in the nonadiabatic decay dynamics of DMNA. After the S₁ 鈫?S₀ decay, the excess kinetic energy finally results in the cleavage of the N鈥揘 bond in the ground electronic state. The two reaction channels through CI_01伪 and CI_01尾 show differences in molecular motions and decay features. The trajectories passing CI_01伪 can hop one or several times, and the intramolecular vibrational energy transfer in the ground state takes place before dissociation, whereas trajectories following the CI_01尾 channel mainly dissociate directly after only one S₁ 鈫?S₀ hop.