Excited-state dynamics of molecules with classically driven trajectories and Gaussians
Excited-state dynamics of molecules with classically driven trajectories and Gaussians
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DOI：
10.1080/00268976.2019.1665199
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发表时间：
2019-09-20
影响因子：
1.7
通讯作者：
Curchod, Basile F. E.
中科院分区：
文献类型：
--
作者：
Ibele, Lea M.;Nicolson, Angus;Curchod, Basile F. E.
模拟在激发电子态下启动的分子动力学对于理论和计算化学来说是一项相当具有挑战性的任务，因为这种动力学导致核运动和电子态之间的强耦合，即玻恩-奥本海默近似的崩溃。这篇新观点文章简要概述了旨在模拟分子激发态动力学（非绝热分子动力学）的最新理论发展，特别关注采用行进基函数来描绘核波函数动力学的策略。我们首先讨论 Born-Huang 表示中的非绝热分子动力学的中心方程。然后，我们对两种常用策略进行比较，以模拟分子系统在完整构型空间中的激发态动力学，即从头多重生成 (AIMS) 和轨迹表面跳跃 (TSH)。对这两种技术的运动方程进行了比较，并用于对比它们各自对涉及核波包退相干现象的描述。然后总结了 AIMS 方法的一些最新工作和发展。这篇新观点文章的结尾重点介绍了分子波函数的精确因式分解，以及在描述光物理和光化学过程时这种方法与更传统的 Born-Huang 图的对比。
Simulating the dynamics of a molecule initiated in an excited electronic state constitutes a rather challenging task for theoretical and computational chemistry, as such dynamics leads to a strong coupling between nuclear motion and electronic states, that is, a breakdown of the Born-Oppenheimer approximation. This New Views article proposes a brief overview on recent theoretical developments aiming at simulating the excited-state dynamics of molecules - nonadiabatic molecular dynamics - focusing in particular on strategies employing travelling basis functions to portray the dynamics of nuclear wavefunctions. We start by discussing the central equations for nonadiabatic molecular dynamics in a Born-Huang representation. We then propose a comparison between two commonly employed strategies to simulate the excited-state dynamics of molecular systems in their full configuration space, Ab Initio Multiple Spawning (AIMS) and Trajectory Surface Hopping (TSH). The equations of motion for the two techniques are compared and used to contrast their respective description of phenomena involving the decoherence of nuclear wavepackets. Some recent works and developments of the AIMS method are then summarised. This New Views article ends with a highlight on the Exact Factorisation of the molecular wavefunction and how this approach contrasts with the more conventional Born-Huang picture when it comes to the description of photophysical and photochemical processes.