Takahashi Hideaki, Borrelli Raffaele
DISAFA, University of Torino, Grugliasco I10095, Italy.
J Chem Theory Comput. 2024 Aug 17. doi: 10.1021/acs.jctc.4c00711.
Hierarchical Equations of Motion (HEOM) in the Tensor-Train (TT) representation is applied to study the charge-transfer dynamics in organic semiconductors (OSCs). The theoretical formulation as well as the basic computational aspects of HEOM-TT are discussed in detail. Charge transfer in OSCs is modeled using dissipative polaronic models that incorporate the effects of both high- and low-frequency molecular vibrations, and it is simulated in a fully quantum and nonperturbative manner, which has not been studied intensively. The capability of treating complex electron-vibrational systems is examined by analyzing and comparing the numerical behavior of the time-dependent variational approach and the time-Alternating Minimal Energy methods and by calculating the current autocorrelation function and diffusivity across various models. Our results indicate that the HEOM-TT framework offers a robust tool for the detailed analysis of complex polaronic systems, suggesting its potential for broader applications.
张量列车（TT）表示形式下的分层运动方程（HEOM）被应用于研究有机半导体（OSC）中的电荷转移动力学。详细讨论了HEOM-TT的理论公式以及基本计算方面。使用包含高频和低频分子振动效应的耗散极化子模型对OSC中的电荷转移进行建模，并以完全量子和非微扰的方式进行模拟，此前尚未对此进行深入研究。通过分析和比较时间相关变分方法和时间交替最小能量方法的数值行为，并计算各种模型的电流自相关函数和扩散率，来检验处理复杂电子 - 振动系统的能力。我们的结果表明，HEOM-TT框架为复杂极化子系统的详细分析提供了一个强大的工具，表明其具有更广泛应用的潜力。
