First-principles theory of nonlinear long-range electron-phonon interaction

TL;DR

This paper develops a first-principles theoretical framework to describe long-range 1-electron-2-phonon interactions in anharmonic materials, extending beyond the traditional 1-electron-1-phonon models.

Contribution

It derives an analytical expression for the long-range 1-electron-2-phonon matrix element based on microscopic quantities, enabling first-principles calculations of these interactions.

Findings

The long-range 1-electron-2-phonon interaction is linked to the derivative of the phonon dynamical matrix with respect to an electric field.

The quasiparticle energy of a large polaron can be expressed using a 1-electron-2-phonon spectral function.

The effect of 1-electron-2-phonon interaction is small in LiF and KTaO₃, but the framework is general for other materials.

Abstract

Describing electron-phonon interactions in a solid requires knowledge of the electron-phonon matrix elements in the Hamiltonian. State-of-the-art first-principles calculations for the electron-phonon interaction are limited to the 1-electron-1-phonon matrix element, which is suitable for harmonic materials. However, there is no first-principles theory for 1-electron-2-phonon interactions, which occur in anharmonic materials with significant electron-phonon interaction such as halide perovskites and quantum paraelectrics. Here, we derive an analytical expression for the long-range part of the 1-electron-2-phonon matrix element, written in terms of microscopic quantities that can be calculated from first principles. We show that the long-range 1-electron-2-phonon interaction is described by the derivative of the phonon dynamical matrix with respect to an external electric field. We calculate the quasiparticle energy of a large polaron including 1-electron-2-phonon interaction, and show that it can be written in terms of a 1-electron-2-phonon spectral function $\mathcal{T}_{\alpha \beta}(\omega)$. We demonstrate how to calculate this spectral function and its temperature dependence for the benchmark materials LiF and KTaO$_3$, where it turns out that the effect is very small. The first-principles framework developed in this article is general, paving the way for future calculations of 1-electron-2-phonon interactions in materials where the effect may be larger.