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Spectroscopic characterization of microscopic hydrogen-bonding disparities in supercritical water

2005; American Institute of Physics; Volume: 123; Issue: 15 Linguagem: Inglês

10.1063/1.2064867

1520-9032

Philippe Wernet, Denis Testemale, Jean‐Louis Hazemann, R. Argoud, Pieter Glatzel, Lars G. M. Pettersson, Anders Nilsson, Uwe Bergmann,

Analytical Chemistry and Chromatography

The local hydrogen-bonding environment in supercritical water (380°C, 300bars, density 0.54g∕cm3) was studied by x-ray Raman scattering at the oxygen K edge. The spectra are compared to those of the gas phase, liquid surface, bulk liquid, and bulk ice, as well as to calculated spectra. The experimental model systems are used to assign spectral features and to quantify specific local hydrogen-bonding situations in supercritical water. The first coordination shell of the molecules is characterized in more detail with the aid of the calculations. Our analysis suggests that ∼65% of the molecules in supercritical water are hydrogen bonded in configurations that are distinctly different from those in liquid water and ice. In contrast to liquid water the bonded molecules in supercritical water have four intact hydrogen bonds and in contrast to ice large variations of bond angles and distances are observed. The remaining ∼35% of the molecules exhibit two free O–H bonds and are thus either not involved in hydrogen bonding at all or have one or two hydrogen bonds on the oxygen side. We determine an average O–O distance of 3.1±0.1Å in supercritical water for the H bonded molecules at the conditions studied here. This and the corresponding hydrogen bond lengths are shown to agree with neutron- and x-ray-diffraction data at similar conditions. Our results on the local hydrogen-bonding environment with mainly two disparate hydrogen-bonding configurations are consistent with an extended structural model of supercritical water as a heterogeneous system with small patches of bonded molecules in various tetrahedral configurations and surrounding nonbonded gas-phase-like molecules.