Time-dependent quantum wave-packet description of the 1pi sigma* photochemistry of pyrrole.
Time-dependent quantum wave-packet description of the 1pi sigma* photochemistry of pyrrole.
复制标题
吡咯 1pi sigma* 光化学的时间相关量子波包描述。
DOI：
10.1039/b402979h
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发表时间：
2004
影响因子：
3.4
通讯作者：
W. Domcke
中科院分区：
文献类型：
--
作者：
V. Vallet;Z. Lan;S. Mahapatra;A. Sobolewski;W. Domcke
用含时量子波包动力学方法研究了吡咯分子中1B1（1pi sigma*）激发态与电子基态的锥形交叉光诱导氢消除反应.采用多参考从头计算电子结构方法，构造了NH伸缩和氢离面弯曲模的二维模型势能面。在锥形交叉反应通量的分支比已被调查依赖于分子的初始振动状态。结果表明，通过模式特定的振动激发激光控制的光解吡咯应该是可能的。
The photoinduced hydrogen elimination reaction in pyrrole via the conical intersection of the 1B1 (1pi sigma*) excited state with the electronic ground state has been investigated by time-dependent quantum wave-packet dynamics. A two-dimensional model potential-energy surface has been constructed as a function of the NH stretching and the hydrogen out-of-plane bending mode, employing multi-reference ab initio electronic-structure methods. The branching ratio of the reactive flux at the conical intersection has been investigated in dependence on the initial vibrational state of the molecule. The results suggest that laser control of the photodissociation of pyrrole via mode-specific vibrational excitation should be possible.