Strong Exciton-Vibrational Coupling in Molecular Assemblies. Dynamics using the Polaron Transformation in HEOM Space

TL;DR

This paper introduces a novel application of the polaron transformation within the Hierarchical Equations of Motion framework to better understand exciton-vibrational interactions in molecular assemblies, revealing significant effects on transfer dynamics.

Contribution

It develops a new method combining polaron transformation with HEOM for open quantum systems, enabling detailed study of vibrational effects on exciton dynamics in molecular aggregates.

Findings

Polaron transformation significantly influences exciton transfer dynamics.

The basis choice (local vs exciton) affects vibrational localization.

The approach can be used to improve emission spectrum calculations.

Abstract

In the context of Frenkel exciton dynamics in aggregated molecules the polaron transformation technique facilitates a treatment where diagonal elements attributed to electronic excited-state populations are decoupled from fluctuations associated with vibrational degrees-of-freedom. In this article we describe for the first time how the polaron transformation can be applied in the context of the "Hierarchical Equations of Motion" (HEOM) technique for treatment of open quantum systems with all vibrational components attributed to an environment. By using a generating function approach to introduce a shift in the excited state potential energy surface, we derive hierarchical equations for polaron transformation in analogy to those for time propagation. We demonstrate the applicability of the developed approach by calculating the dynamics of underdamped and overdamped oscillators coupled to electronic excitation of a monomer without and with previous polaron transformation and study the dynamics of the expectation value of the respective vibrational coordinates. Furthermore, we investigate the dynamics of a dimer with a barrier comparable to the thermal energy between the minima of the lower excitonic potential energy surface. It turns out that the assumption of localization at the monomer unit with energetically higher potential minimum, introduced via polaron transformation, has a substantial influence on the transfer dynamics. Here, it makes a clear difference whether the polaron transformation is performed in the local or exciton basis. This reflects the fact that the polaron transformation only accounts for equilibration of the vibrational, but not of the excitonic dynamics. We sketch an approach to compensate this shortcoming in view of obtaining an initial state for the calculation of emission spectra of molecular aggregates.