Phonon effects on x-ray absorption and nuclear magnetic resonance spectroscopies
Résumé
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-principles
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 quasiharmonic approximations, we incorporate the
nuclear motion by generating several nonequilibrium configurations from the dynamical matrix. The averaged
calculated XANES and NMR spectral data have been compared to experiments in MgO. 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 nonequilibrium configurations is a suitable
approximation. This study highlights 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.