Phonon effects on x-ray absorption and nuclear magnetic resonance spectroscopies

Abstract

In material sciences, spectroscopic approaches combining ab initio calculations with experiments are commonly used to accurately analyze the experimental spectral data. Most state-of-the-art first-principle calculations are usually performed assuming an equilibrium static lattice. Yet, nuclear motion affects spectra even when reduced to the zero-point motion at 0 K. We propose a framework based on Density-Functional Theory that includes quantum thermal fluctuations in theoretical X- ray Absorption Near-Edge Structure (XANES) and solid-state Nuclear Magnetic Resonance (NMR) spectroscopies and allows to well describe temperature effects observed experimentally. Within the Born-Oppenheimer and quasi-harmonic approximations, we incorporate the nuclear motion by generating several non-equilibrium configurations from the dynamical matrix. The averaged calculated XANES and NMR spectral data have been compared to experiments in MgO, proof-of-principle compound. The good agreement obtained between experiments and calculations validates the developed approach, which suggests that calculating the XANES spectra at finite temperature by averaging individual non-equilibrium configurations is a suitable approximation. This study high- lights the relevance of phonon renormalization and the relative contributions of thermal expansion and nuclear dynamics on NMR and XANES spectra on a wide range of temperatures.