A Reciprocal-Space Formulation of Mixed Quantum-Classical Dynamics

TL;DR

This paper develops a reciprocal-space formulation for mixed quantum-classical dynamics to efficiently model electron-phonon interactions, verified through models and enabling low-momentum carrier simulations.

Contribution

It introduces a reciprocal-space formalism for mixed quantum-classical dynamics, providing a computationally efficient approach for modeling electron-phonon interactions.

Findings

Reciprocal-space formalism is equivalent to real-space mean-field dynamics.

For Holstein and Peierls models, reciprocal-space forces include momentum derivatives.

Truncated reciprocal basis enables inexpensive low-momentum carrier modeling.

Abstract

We derive a formulation of mixed quantum-classical dynamics for describing electronic carriers interacting with phonons in reciprocal space. For dispersionless phonons, we start by expressing the real-space classical coordinates in terms of complex variables. A Fourier series over these coordinates then yields the reciprocal-space coordinates. Evaluating the electron-phonon interaction term through Ehrenfest's theorem, we arrive at a reciprocal-space formalism that is equivalent to mean-field mixed quantum-classical dynamics in real space. This equivalence is numerically verified for the Holstein and Peierls models, for which we find the reciprocal-space Hellmann-Feynman forces to involve momentum derivative contributions in addition to the position derivative terms commonly seen in real space. We close by presenting a proof of concept for the inexpensive modeling of low-momentum carriers interacting with phonons by means of a truncated basis in reciprocal space, which is not possible within a real space formulation.