Role of quantum nuclei and local fields in the x-ray absorption spectra of water and ice

Abstract

We calculate the x-ray absorption spectra of liquid water at ambient conditions and of hexagonal ice close to melting, using a static GW approach that includes approximately local field effects. Quantum dynamics of the nuclei is taken into account by averaging the absorption cross section over molecular configurations generated by path integral simulations. We find that inclusion of quantum disorder is essential to bring the calculated spectra in close agreement with experiment. In particular, the intensity of the pre-edge feature, a spectral signature of broken and distorted hydrogen bonds, is accurately reproduced, in water and ice, only when quantum nuclei are considered. The effect of the local fields is less important but non negligible, particularly in ice.

References in corpus (4)

• Nuclear quantum effects in water
• Bethe-Salpeter Equation Calculations of Core Excitation Spectra
• Theoretical optical and x-ray spectra of liquid and solid H_2O
• Momentum distribution, vibrational dynamics and the potential of mean force in ice

Cited by in corpus (15)

• The Individual and Collective Effects of Exact Exchange and Dispersion Interactions on the Ab Initio Structure of Liquid Water
• Electronic signature of the instantaneous asymmetry in the first coordination shell of liquid water
• Simulation and understanding of quantum crystals
• Recent achievements in ab initio modelling of liquid water
• Electron-hole theory of the effect of quantum nuclei on the x-ray absorption spectra of liquid water
• Efficient Simulation of Near-Edge X-ray Absorption Fine Structure (NEXAFS) in Density-Functional Theory: Comparison of Core-Level Constraining Approaches
• Simulation of quantum zero-point effects in water using a frequency-dependent thermostat
• Many-Body Effects in the X-ray Absorption Spectra of Liquid Water
• Ab initio studies of ionization potentials of hydrated hydroxide and hydronium
• Nuclear Quantum Effects in Liquid Water Are Negligible for Structure but Significant for Dynamics
• Tumbling with a Limp: Local Asymmetry in Water's Hydrogen Bond Network and its Consequences
• Nuclear quantum effects on the quasiparticle properties of the chloride anion aqueous solution within the GW approximation
• X-ray absorption of liquid water by advanced ab initio methods
• Isotope effects in x-ray absorption spectra of liquid water
• Exploring the Impact of Ions on Oxygen K-Edge X-ray Absorption Spectroscopy in NaCl Solution using the GW-Bethe-Salpeter-Equation Approach