Nonadiabatic quantum molecular dynamics with hopping. III. Photoinduced excitation and relaxation of organic molecules
Nonadiabatic quantum molecular dynamics with hopping. III. Photoinduced excitation and relaxation of organic molecules
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具有跳跃 III 的非绝热量子分子动力学 有机分子的光致激发和弛豫
DOI：
10.1103/physreva.90.012527
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发表时间：
2014
影响因子：
2.9
通讯作者：
R. Schmidt
中科院分区：
文献类型：
--
作者：
M. Fischer;J. Handt;R. Schmidt
通过最近开发的具有跳跃的非绝热量子分子动力学（NA-QMD-H）研究有机分子（和）的光诱导激发和弛豫[Fischer，Handt和施密特，该系列的论文I，Phys.Rev.A90，012525（2014）PLRAAN 1050 -294710.1103/PhysRevA.90.012525]。该方法首先应用于假定分子初始处于电子表面的自激态。特别注意阐述电子-核关联的作用，即，原子核动力学中的量子效应结果发现，它们是必不可少的一个现实的描述的电子弛豫过程的长时间的行为，但只有次要的重要性，描绘的核动力学的短时间的情况。然而，氢原子的迁移被认为是核运动中的量子效应。得到的结果与明确列入FS激光场。结果表明，激光诱导的激发过程一般会导致定性不同的总功能的弛豫动力学，相比无场的情况下。然而，在没有激光场的情况下，原子核的波包包含了所有的反式异构化机制。
Photoinduced excitation and relaxation of organic molecules (and) are investigated by means of nonadiabatic quantum molecular dynamics with hopping (NA-QMD-H), developed recently [Fischer, Handt, and Schmidt, paper I of this series, Phys. Rev. A 90, 012525 (2014)PLRAAN1050-294710.1103/PhysRevA.90.012525]. This method is first applied to molecules assumed to be initiallyad hocexcited to an electronic surface. Special attention is drawn to elaborate the role of electron-nuclear correlations, i.e., of quantum effects in the nuclear dynamics. It is found that they are essential for a realistic description of the long-time behavior of the electronic relaxation process, but only of minor importance to portray the short-time scenario of the nuclear dynamics. Migration of a hydrogen atom, however, is identified as a quantum effect in the nuclear motion. Results obtained with explicit inclusion of an fs-laser field are presented as well. It is shown that the laser-induced excitation process generally leads to qualitatively different gross features of the relaxation dynamics, as compared to the field-free case. Nevertheless, the nuclear wave packet contains all subtleties of thecis-transisomerization mechanism as observed without a laser field.