A quantum perturbative pair distribution for determining interatomic potentials from extended X-ray absorption spectroscopy

Abstract

In this paper we develop a technique for determining interatomic potentials in materials in the quantum regime from single--shell Extended X-ray Absorption Spectroscopy (EXAFS) spectra. We introduce a pair distribution function, based on ordinary quantum time--independent perturbation theory. In the proposed scheme, the model potential parameters enter the distribution through a fourth--order Taylor expansion of the potential, and are directly refined in the fit of the model signal to the experimental spectrum. We discuss in general the validity of our theoretical framework, namely the quantum regime and perturbative treatment, and work out a simple tool for monitoring the sensitivity of our theory in determining lattice anharmonicities based on the statistical $F$--test. As an example, we apply our formalism to an EXAFS spectrum at the Ag K--edge of AgI at T=77 K. We determine the Ag--I potential parameters and find good agreement with previous studies.