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.

arXiv comment13 pages, 6 figures, 1 appendix

References in corpus (18)

• Quantum ESPRESSO: a modular and open-source software project for quantum simulations of materials
• Restoring the density-gradient expansion for exchange in solids and surfaces
• Generalized gradient approximation for solids and their surfaces
• Phonons and related properties of extended systems from density-functional perturbation theory
• A More Accurate Generalized Gradient Approximation for Solids
• All-electron magnetic response with pseudopotentials: NMR chemical shifts
• An Efficient and Accurate Car-Parrinello-like Approach to Born-Oppenheimer Molecular Dynamics
• Anharmonic free energies and phonon dispersions from the stochastic self-consistent harmonic approximation: application to platinum and palladium hydrides
• Thermal properties of materials from ab-initio quasi-harmonic phonons
• X-ray Absorption Near-Edge Structure calculations with pseudopotentials. Application to K-edge in diamond and alpha-quartz
• First-Principles Theory of Anharmonicity and the Inverse Isotope Effect in Superconducting Palladium-Hydride Compounds
• Accuracy of generalized gradient approximation functionals for density functional perturbation theory calculations
• Anharmonic vibrational properties in periodic systems: energy, electron-phonon coupling, and stress
• The temperature dependence of electronic eigenenergies in the adiabatic harmonic approximation
• Experimental evidence of thermal fluctuations on the X-ray absorption near-edge structure at the aluminum K-edge
• Effect of vibrations on the pre-edge features of x-ray absorption spectra
• Temperature effects in first-principles solid state calculations of the chemical shielding tensor made simple
• Temperature dependence of the pre-edge structure in the Ti K-edge x-ray absorption spectrum of rutile

Cited by in corpus (7)

• Vibrational Effects in X-ray Absorption Spectra of 2D Layered Materials
• Multi-scale theoretical approach to X-ray absorption spectra in disordered systems: an application to the study of Zn(II) in water
• Real-space Green's function approach for x-ray spectra at finite temperature
• Nuclear magnetic resonance spectroscopy as a dynamical structural probe of high pressure hydrogen
• Resonant X-ray Emission and Valence-band Lifetime Broadening in LiNO${}_3$
• Stochastic sampling of quadrature grids for the evaluation of vibrational expectation values
• Effect of lattice excitations on transient near edge X-ray absorption spectroscopy