Electron-phonon couplings in polymorphous crystals

Abstract

Positional polymorphism in solids refers to locally disordered unit cells that, on average, reproduce the high-symmetry structures observed in diffraction experiments. Standard theories of electron-phonon interactions fail to describe the temperature-dependent electronic structure of such polymorphous systems. Hybrid halide perovskites are a prime example, where configurational entropy from both polymorphism and molecular disorder plays a central role. Here we generalize the special displacement method to polymorphous crystals, providing an efficient ab initio framework for electron-phonon couplings without resorting to molecular dynamics. We resolve long-standing discrepancies in hybrid halide perovskite physics, including temperature-dependent anharmonic phonons and band gaps. Our approach provides a practical route to link local disorder, configurational entropy, and electron-phonon interactions, with applicability across diverse material classes, from optoelectronics and ferroelectrics to thermoelectrics.