Nonadiabatic dynamics with quantum nuclei: simulating charge transfer with ring polymer surface hopping.,Faraday Discussions

当前位置： X-MOL 学术 › Faraday Discuss. › 论文详情

Our official English website, www.x-mol.net, welcomes your feedback! (Note: you will need to create a separate account there.)

Nonadiabatic dynamics with quantum nuclei: simulating charge transfer with ring polymer surface hopping.
Faraday Discussions ( IF 3.3 ) Pub Date : 2019-12-16 , DOI: 10.1039/c9fd00046a
Soumya Ghosh ₁ , Samuele Giannini , Kevin Lively , Jochen Blumberger

Affiliation

Investigation of many electronic processes in molecules and materials, such as charge and exciton transport, requires a computational framework that incorporates both non-adiabatic electronic effects and nuclear quantum effects, in particular at low temperatures. We have recently developed an efficient semi-empirical fewest switches surface hopping method, denoted fragment orbital-based surface hopping (FOB-SH), that was tailored towards highly efficient simulation of charge transport in molecular materials, yet with nuclei treated classically. In this work, we extend FOB-SH and include nuclear quantum effects by combining it with ring-polymer molecular dynamics (RPMD) in three different flavours: (i) RPSH with bead approximation (RPSH-BA) as suggested in Shushkov et al., J. Chem. Phys., 2012, 137, 22A549, (ii) a modification of (i) denoted RPSH with weighted bead approximation (RPSH-wBA) and (iii) the isomorphic Hamiltonian method of Tao et al., J. Chem. Phys., 2018, 148, 10237 (SH-RP-iso). We present here applications to hole transfer in a molecular dimer model and analyze detailed balance and internal consistency of all three methods and investigate the temperature and driving force dependence of the hole transfer rate. We find that RPSH-BA strongly underestimates and RPSH-wBA overestimates the exact excited state population, while SH-RP-iso gives satisfactory results. We also find that the latter predicts a flattening of the rate vs. driving force dependence in the Marcus inverted regime at low temperature, as often observed experimentally. Overall, our results suggest that FOB-SH combined with SH-RP-iso is a promising method for including zero point motion and tunneling in charge transport simulations in molecular materials and biological systems.

中文翻译：

带有量子核的非绝热动力学：利用环状聚合物表面跳跃模拟电荷转移。

研究分子和材料中的许多电子过程，例如电荷和激子传输，需要一个计算框架，该框架应兼具非绝热电子效应和核量子效应，尤其是在低温下。我们最近开发了一种有效的半经验最少的开关表面跳变方法，称为基于碎片轨道的表面跳变（FOB-SH），该方法专门用于分子材料中电荷传输的高效模拟，并且对核进行了经典处理。在这项工作中，我们扩展了FOB-SH并通过将它与环状聚合物分子动力学（RPMD）结合在三种不同的风味中来包括核量子效应：（i）如Shushkov等人所述，带珠近似的RPSH（RPSH-BA）。，J. Chem。物理。，2012，137，22A549，（ii）（i）用加权磁珠近似（RPSH-wBA）表示的RPSH和（iii）Tao等人在《化学学报》（J. Chem。物理.2018，148，10237（SH-RP-iso）。我们在此介绍分子二聚体模型中空穴传输的应用，并分析所有三种方法的详细平衡和内部一致性，并研究温度和驱动力对空穴传输速率的依赖性。我们发现RPSH-BA严重低估了RPSH-wBA并高估了确切的激发态种群，而SH-RP-iso给出了令人满意的结果。我们还发现，后者可以预测在低温下Marcus倒置状态下速率与驱动力的依赖关系会趋于平缓，这在实验中经常观察到。全面的，

更新日期：2019-12-17

点击分享查看原文

点击收藏

公开下载

阅读更多本刊最新论文本刊介绍/投稿指南11