Photo-induced reactions from efficient molecular dynamics with electronic transitions using the FIREBALL local-orbital density functional theory formalism
Photo-induced reactions from efficient molecular dynamics with electronic transitions using the FIREBALL local-orbital density functional theory formalism
复制标题
使用 FIREBALL 局域轨道密度泛函理论形式从有效分子动力学和电子跃迁中产生光诱导反应
DOI：
10.1088/0953-8984/27/17/175002
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发表时间：
2014
期刊：
影响因子：
--
通讯作者：
J. Ortega
中科院分区：
文献类型：
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作者：
Vladimír Zobač;James P. Lewis;E. Abad;J. I. Mendieta;P. Hapala;P. Jelínek;J. Ortega
光诱导过程在大分子体系中的计算模拟是一个非常具有挑战性的问题。首先，为了正确地模拟光诱导反应，必须适当地访问激发态对应的势能面；其次，理解这些过程的机制需要对复杂构型空间的探索和圆锥交叉口的定位；最后，光诱导反应是概率事件，需要模拟数百个轨迹来获得分析反应曲线的统计信息。在这里，我们详细描述了我们在局部轨道密度泛函理论代码FIREBALL中实现的带有电子跃迁的分子动力学算法，适合于这些问题的计算研究。作为该方法应用的一个例子，我们还报道了乙烯与马来酸酐的[2 + 2]环加成反应和两个C60分子的[2 + 2]光诱导聚合反应的结果。根据电子从LUMO跃迁到HOMO的时间和跃迁后HOMO的性质，我们确定了初始电子激发的不同失活通道。
The computational simulation of photo-induced processes in large molecular systems is a very challenging problem. Firstly, to properly simulate photo-induced reactions the potential energy surfaces corresponding to excited states must be appropriately accessed; secondly, understanding the mechanisms of these processes requires the exploration of complex configurational spaces and the localization of conical intersections; finally, photo-induced reactions are probability events, that require the simulation of hundreds of trajectories to obtain the statistical information for the analysis of the reaction profiles. Here, we present a detailed description of our implementation of a molecular dynamics with electronic transitions algorithm within the local-orbital density functional theory code FIREBALL, suitable for the computational study of these problems. As an example of the application of this approach, we also report results on the [2 + 2] cycloaddition of ethylene with maleic anhydride and on the [2 + 2] photo-induced polymerization reaction of two C60 molecules. We identify different deactivation channels of the initial electron excitation, depending on the time of the electronic transition from LUMO to HOMO, and the character of the HOMO after the transition.