Numerically "exact" charge transport dynamics in a dissipative electron-phonon model rationalizing the success of the transient localization scenario

TL;DR

This paper uses advanced numerical methods to analyze charge transport in molecular semiconductors, confirming that transient localization explains experimental optical conductivity features and clarifying the role of damping and phonon interactions.

Contribution

It introduces the dissipaton equations of motion (DEOM) approach to accurately simulate charge transport, demonstrating the robustness of the transient localization phenomenology across damping regimes.

Findings

Optical conductivity profiles become similar to TL predictions with increased damping.

Transient localization phenomenology is valid even in underdamped oscillator regimes.

Low-frequency optical-conductivity enhancements are artifacts of simplified phonon models.

Abstract

Optical conductivity in molecular semiconductors is suppressed in the terahertz region, featuring the displaced Drude peak that reflects carriers' transient localization (TL) by slow intermolecular vibrations. Meanwhile, recent computations in minimal models evidence optical-conductivity enhancements below the characteristic vibrational frequency, which cannot be captured by the TL phenomenology. These models assume that the carrier's hopping amplitude is modulated by a single undamped vibration. The modulation is, however, by many low-frequency modes, whose net effect can be approximated using a few effective damped oscillators. Here, we employ the dissipaton equations of motion (DEOM) method to compute the finite-temperature real-time current autocorrelation function in a one-dimensional model with Brownian-oscillator spectral density of nonlocal carrier-phonon interaction. We exploit the dissipaton algebra to handle the phonon-assisted current, reduce the method's computational requirements by working in momentum space, and confirm that numerically stable transport dynamics are virtually independent of a specific DEOM closing scheme. With increasing damping, we find that DEOM optical-conductivity profiles become increasingly qualitatively similar to TL predictions. For parameters representative of room-temperature hole transport in single-crystal rubrene, we conclude that the TL phenomenology is established already in the underdamped-oscillator regime. Reasonable variations in the damping constant weakly affect the carrier mobility, which remains within experimental bounds. Overall, our results strongly suggest that optical-conductivity enhancements at very low frequencies are artifacts of the assumed delta-like phonon spectrum and rationalize the success of the TL phenomenology in describing experimental data.