Vinicius Vaz da Cruz, Sebastian Eckert, Marcella Iannuzzi, Emelie Ertan, Annette Pietzsch, Rafael C. Couto, Johannes Niskanen, Mattis Fondell, Marcus Dantz, Thorsten Schmitt, Xingye Lu, Daniel McNally, Raphael Martin Jay, Victor Kimberg, Alexander Föhlisch, Michael Odelius

• Local probes of the electronic ground state are essential for understanding hydrogen bonding in aqueous environments. When tuned to the dissociative core-excited state at the O1s pre-edge of water, resonant inelastic X-ray scattering back to the electronic ground state exhibits a long vibrational progression due to ultrafast nuclear dynamics. We show how the coherent evolution of the OH bonds around the core-excited oxygen provides access to high vibrational levels in liquid water. The OH bonds stretch into the long-range part of the potential energy curve, which makes the X-ray probe more sensitive than infra-red spectroscopy to the local environment. We exploit this property to effectively probe hydrogen bond strength via the distribution of intramolecular OH potentials derived from measurements. In contrast, the dynamical splitting in the spectral feature of the lowest valence-excited state arises from the short-range part of the OH potential curve and is rather insensitive to hydrogen bonding.