Coherent and Incoherent Time-Resolved Diffuse Scattering Intensity from First Principles

Abstract

Time-resolved diffuse scattering from X-ray free-electron lasers and ultrafast electron diffraction gives access to the nonequilibrium lattice dynamics of photoexcited solids in reciprocal space. Existing interpretations have often relied on simplified models. Here we present a first-principles formulation of the time-dependent first-order diffuse intensity in which coherent and incoherent contributions emerge on equal footing. By assuming the probe-pulse coherence time to be longer than the characteristic electronic timescales, but shorter than those of the ionic motion, we work in the density-matrix formalism and derive equations of motion for the displacement-displacement correlators in a basis of instantaneous, out-of-equilibrium Born-Oppenheimer normal modes. We show how the incoherent contribution, governed by the phonon occupations, and a coherent contribution, governed by the anomalous phonon correlators, emerge. The non-trivial coherent dynamics is shown to be induced both by the photoinduced phonon-frequency shift and by electron-phonon scattering off the nonequilibrium carrier distribution. We implement the resulting equations using Wannier interpolation in the \textsc{EPI}q code and apply them to photoexcited germanium. The calculated diffuse intensity reproduces both the oscillation frequencies and the rising incoherent background observed experimentally, opening the way to a systematic interpretation of time-resolved diffuse scattering in ultrafast experiments.