Inhomogeneous Evolution of a Dense Ensemble of Optically Pumped Excitons to a Charge Transfer State

TL;DR

This paper models the complex spatio-temporal dynamics of optically pumped excitons in organic compounds, revealing how exciton self-trapping and domain formation lead to phase transformations akin to excitonic insulator behavior.

Contribution

It introduces a semi-phenomenological model capturing the interplay of exciton dynamics, self-trapping, and phase transitions in systems with intermolecular electronic transfer.

Findings

Exciton self-trapping can locally trigger phase transformations.

Domains formed during the transition can persist after exciton recombination.

The model links exciton density to phase change mechanisms.

Abstract

Phase transformations induced by short optical pulses are mainstream in studies on the dynamics of cooperative electronic states. We present a semi-phenomenological modeling of spacio-temporal effects expected when optical excitons are intricate with the order parameter as in, e.g., organic compounds with neutral-ionic ferroelectric phase transitions. A conceptual complication appears here, where both the excitation and the ground state ordering are built from the intermolecular electronic transfer. To describe both thermodynamic and dynamic effects on the same root, we adopt, for the phase transition, a view of the Excitonic Insulator - a hypothetical phase of a semiconductor that appears if the exciton energy becomes negative. After the initial pumping pulse, a quasi-condensate of excitons can appear as a macroscopic quantum state that then evolves, while interacting with other degrees of freedom which are prone to an instability. The self-trapping of excitons enhances their density, which can locally surpass a critical value to trigger the phase transformation. The system is stratified in domains that evolve through dynamical phase transitions and may persist even after the initiating excitons have recombined.