Comparison of Matrix Product State and Multiconfiguration Time-Dependent Hartree Methods for Nonadiabatic Dynamics of Exciton Dissociation.

Abstract

The excited-state dynamics of organic molecules, molecular aggregates, and donor-acceptor clusters is typically governed by the interplay of electronic excitations and, due to their flexibility and soft bonding, by the interaction with their vibrations. This interaction in these systems can be characterized by a few relevant electronic states that are coupled to numerous vibrational normal modes, encompassing a vast configurational space of the molecules. The full quantum simulation of these type of systems has been long dominated by the multiconfiguration time-dependent Hartree (MCTDH) approach and its multilayer variants, which are considered the gold standard in the presence of electron-vibration coupling with a large number of modes. Recently, also the matrix product state ansatz (MPS) with appropriate time-evolution schemes has been applied to these types of Hamiltonians. In this article, we provide a numerical comparison of excited-state dynamics between the MCTDH and MPS approaches for two electron-vibration coupled systems. Notably, we consider two models for exciton dissociation at a P3HT:PCBM heterojunction, comprising two electronic states and 100 vibrational modes, and 26 electronic states and 113 vibrational modes, respectively. While both methods agree very well for the first model, more pronounced deviations are found for the second model. We trace back the divergence between the methods to the different way entanglement is treated.