论文标题

一维荷斯坦模型中的实时非绝热动态:基于轨迹的与精确方法

Real-time non-adiabatic dynamics in the one-dimensional Holstein model: Trajectory-based vs exact methods

论文作者

Brink, Michael ten, Gräber, Stefan, Hopjan, Miroslav, Jansen, David, Stolpp, Jan, Heidrich-Meisner, Fabian, Blöchl, Peter E.

论文摘要

我们基准了一组量子化学方法,包括多个原则eHrenfest,最少的开关表面跳跃和多构型eHrenrenfest动力学,通过研究荷尔斯坦模型中的实时动力学来针对精确的量子 - 体型技术。这是凝结物质理论中的范式模型,该模型结合了电子与爱因斯坦语音子的局部耦合。对于两个站点和三个位点荷斯坦模型,我们讨论了符合人类形式主义的确切和量子化学方法,涵盖了不同的初始状态,该状态既始于单个Born-oppenheimer表面,也可以与电子定位于单个位点开始。对于具有多达51个位点的扩展系统,我们既解决了单个荷尔斯坦极化物的物理学,又解决有限电子密度下电荷密度波的动力学。对于这些扩展系统,我们将量子化学方法与从局部基础优化(DMRG-LBO)获得的量子化学方法与从时间依赖性密度矩阵重质化组计算获得的精确动力学进行了比较。我们观察到,通常可以准确捕获超短时动力学的多标点EHRENFEST方法。相比之下,具有合适校正的表面跳跃方法可以更好地描述长期行为,但与对不同Born-Oppenheimer态之间的连贯性的短期描述斗争。我们表明,多构型eHrenfest方法对多个原则Ehrenfest方法产生了显着改善,并且可以在具有适度计算工作的小型系统中收集到确切的结果。我们进一步观察到,对于扩展系统,相对于配置数量,这种收敛性较慢。我们的基准研究表明,DMRG-LBO是评估量子化学方法质量的有用工具。

We benchmark a set of quantum-chemistry methods, including multitrajectory Ehrenfest, fewest-switches surface-hopping, and multiconfigurational-Ehrenfest dynamics, against exact quantum-many-body techniques by studying real-time dynamics in the Holstein model. This is a paradigmatic model in condensed matter theory incorporating a local coupling of electrons to Einstein phonons. For the two-site and three-site Holstein model, we discuss the exact and quantum-chemistry methods in terms of the Born-Huang formalism, covering different initial states, which either start on a single Born-Oppenheimer surface, or with the electron localized to a single site. For extended systems with up to 51 sites, we address both the physics of single Holstein polarons and the dynamics of charge-density waves at finite electron densities. For these extended systems, we compare the quantum-chemistry methods to exact dynamics obtained from time-dependent density matrix renormalization group calculations with local basis optimization (DMRG-LBO). We observe that the multitrajectory Ehrenfest method, in general, only captures the ultrashort time dynamics accurately. In contrast, the surface-hopping method with suitable corrections provides a much better description of the long-time behavior but struggles with the short-time description of coherences between different Born-Oppenheimer states. We show that the multiconfigurational Ehrenfest method yields a significant improvement over the multitrajectory Ehrenfest method and can be converged to the exact results in small systems with moderate computational efforts. We further observe that for extended systems, this convergence is slower with respect to the number of configurations. Our benchmark study demonstrates that DMRG-LBO is a useful tool for assessing the quality of the quantum-chemistry methods.

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