Cuts through the manifold of molecular H 2 O potential energy surfaces in liquid water at ambient conditions

Abstract

The fluctuating hydrogen bridge bonded network of liquid water at ambient conditions entails a varied ensemble of the underlying constituting H 2 O molecular moieties. This is mirrored in a manifold of the H 2 O molecular potentials. Subnatural line width resonant inelastic X-ray scattering allowed us to quantify the manifold of molecular potential energy surfaces along the H 2 O symmetric normal mode and the local asymmetric O–H bond coordinate up to 1 and 1.5 Å, respectively. The comparison of the single H 2 O molecular potentials and spectroscopic signatures with the ambient conditions liquid phase H 2 O molecular potentials is done on various levels. In the gas phase, first principles, Morse potentials, and stepwise harmonic potential reconstruction have been employed and benchmarked. In the liquid phase the determination of the potential energy manifold along the local asymmetric O–H bond coordinate from resonant inelastic X-ray scattering via the bound state oxygen 1 s to 4 a 1 resonance is treated within these frameworks. The potential energy surface manifold along the symmetric stretch from resonant inelastic X-ray scattering via the oxygen 1 s to 2 b 2 resonance is based on stepwise harmonic reconstruction. We find in liquid water at ambient conditions H 2 O molecular potentials ranging from the weak interaction limit to strongly distorted potentials which are put into perspective to established parameters, i.e., intermolecular O–H, H–H, and O–O correlation lengths from neutron scattering.