High resolution X-ray emission spectroscopy of water and its assignment based on two structural motifs

Abstract

We evaluate proposed interpretations of previous X-ray emission spectroscopy (XES) data on liquid water. The split peak in the lone-pair orbital region has been interpreted in terms of either two different structural motifs, tetrahedral and distorted, or as due to core-hole-induced dissociative dynamics; here we add new data on a 1:1 H 2O/D 2O isotopic mixture and additional spectrum simulations including the core-hole-induced dynamics. The XES spectrum of HDO is quite nicely reproduced as the sum of spectra of H 2O and D 2O, which we interpret as that core-hole-induced dynamics contribute only to the peak shape and do not affect the intensity ratio between tetrahedrally coordinated and distorted. We find the simulation-based interpretation of the two lone-pair peaks as being of completely different symmetries, molecular 1b 1 and dissociated 3a 1, difficult to reconcile with the experimental intensities in the 1b 2 and 3a 1 spectral regions. We report extensive theoretical simulations of spectra probing both the distance and velocity quantum distributions of the internal OH stretch; sharp features not associated with the lone-pair, that are seen when the OH stretch is treated as a classical oscillator, become smeared out when the zero-point Franck–Condon profile and momentum distribution in the v = 0 level of the OH stretch are taken into account. This demonstrates that neglecting zero-point motion in simulating XES spectra of water generates artificially sharp structures. XES spectra of 1 M and 4 M hydrochloric acid (HCl) and sodium hydroxide (NaOH) are reported. These spectra indicate that dissociated species most likely can be excluded as the origin of the double 1b 1 peak structure. We thus argue that the experimental observation of two distinct peaks in the lone-pair region is less likely to be explained by an unstructured continuum model of the liquid, but is easily explained within a two-component fluctuating model.