期刊
JOURNAL OF CHEMICAL PHYSICS
卷 121, 期 5, 页码 2208-2214出版社
AMER INST PHYSICS
DOI: 10.1063/1.1768171
关键词
-
Photodissociation of diiodomethane (CH2I2) in acetonitrile solution has been studied with ab initio molecular dynamics simulations, which show how the iso-diiodomethane photoproduct (CH2I-I) can be formed. The first excited state, described by the restricted open-shell Kohn-Sham density functional method, is dissociative and photoexcitation of diiodomethane induces a breaking of one of the C-I bonds. In the simulations, we observe that energy dissipation to the surrounding solvent is essential in the formation of a stable iso-diiodomethane molecule. The caging effect of the solvent results in a recombination of the CH2I and I fragments into iso-diiodomethane on a picosecond time scale. The molecular dynamics simulations enable us to study the cage effect as well as the relaxation of intermediates and the distribution of energy. The CH2I fragment is formed vibrationally excited along the C-I stretching mode. After recombination of the CH2I and I fragments, iso-diiodomethane shows a strong vibration excitation in the CH2 group, which could be used as a fingerprint of the proposed mechanism. (C) 2004 American Institute of Physics.
作者
我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。
推荐
暂无数据