Advanced Capabilities of the PYXAID Program: Integration Schemes, Decoherenc:e Effects, Multiexcitonic States, and Field-Matter Interaction
Advanced Capabilities of the PYXAID Program: Integration Schemes, Decoherenc:e Effects, Multiexcitonic States, and Field-Matter Interaction
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DOI：
10.1021/ct400934c
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发表时间：
2014-02-01
影响因子：
5.5
通讯作者：
Prezhdo, Oleg V.
中科院分区：
文献类型：
--
作者：
Akimov, Alexey V.;Prezhdo, Oleg V.
在我们以前的工作中[J.Chem.理论计算。2013，9,4959]，我们介绍了PYXAID程序，该程序是为在大规模凝聚态系统中进行非绝热分子动力学模拟而开发的。该计划的方法学方面和基本能力得到了广泛的讨论。在目前的工作中，我们对该程序的高级能力进行了深入的研究，即，对含时薛定谔方程(TD-SE)的高级积分技术，通过退相干诱导的表面跳跃进行的退相干校正，使用多激子基组态，以及通过显式光-物质相互作用直接模拟光激发。我们通过研究各种系统中的电子动力学来证明上述特征的重要性。特别是，我们证明了用于求解TD-SE的先进的积分技术可以显著地加速计算，并提供更稳定的解。我们证明了退相干对于准确描述固体C-60中的电子-空穴复合等慢弛豫过程是必要的。通过使用多激子组态和场-物质相互作用的直接、非微扰处理，。我们发现了小硅团簇中多激子产生的非平凡最优性条件。
In our previous work [J. Chem. Theory Comput. 2013, 9, 4959], we introduced the PYXAID program, developed for the purpose of performing nonadiabatic molecular dynamics simulations in large-scale condensed matter systems. The methodological aspects and the basic capabilities of the program have been extensively discussed. In the present work, we perform a thorough investigation of advanced capabilities of the program, namely, the advanced integration techniques for the time-dependent Schrodinger equation (TD-SE), the decoherence corrections via decoherence-induced surface hopping, the use of multiexciton basis configurations, and the direct simulation of photoexcitation via explicit light-matter interaction. We demonstrate the importance of the mentioned features by studying the electronic dynamics in a variety of systems. In particular, we demonstrate that the advanced integration techniques for solving TD-SE may lead to a significant speedup of the calculations and provide more stable solutions. We show that decoherence is necessary for accurate description of slow relaxation processes such as electron-hole recombination in solid C-60. By using multiexciton configurations and direct, nonperturbative treatment of field-matter interactions,. we found nontrivial optimality conditions for the multiple exciton generation in a small silicon cluster.