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

TL;DR

This paper benchmarks various quantum-chemistry methods against exact techniques for simulating real-time non-adiabatic dynamics in the Holstein model, revealing strengths and limitations of each approach in different system sizes and conditions.

Contribution

It provides a comprehensive comparison of trajectory-based quantum-chemistry methods with exact DMRG-LBO results for the Holstein model, highlighting their accuracy and convergence properties.

Findings

Multitrajectory Ehrenfest captures short-time dynamics well.

Surface-hopping improves long-time behavior but struggles with initial coherences.

Multiconfigurational Ehrenfest converges to exact results in small systems.

Abstract

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.