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

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 ${\mathcal{T}}_{\hat{I}\pm {\hat{I}}^2}(\ddot{I}‰)$. 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.

37 pages, 10 figures. Accepted for publication in Physical Review B. Merger of a previous version with arXiv:2412.09456, which has been withdrawn from arXiv. All results of arXiv:2412.09456 are reproduced here unchanged