title: Strong intermolecular coupling between the HF stretching and H2O bending vibrations in HF:H2O binary amorphous solids: breakdown of the electrostatic description of the hydrogen bond.
abstract: The coupling mechanism between the HF stretching and H(2)O bending vibrations observed in the infrared spectra of HF:H(2)O binary amorphous solids is analyzed using a simple cluster model. The intermolecular vibrational coupling derived from electrostatic potentials is one order of magnitude smaller, and of the opposite sign, than that obtained from electronic structure-based potentials. This highlights the distinctively covalent character of strong H-bonds and unveils fundamental weaknesses of electrostatic descriptions of vibrational energy transfer in liquid water and aqueous solutions.
authors.affiliation: Département de chimie, Université de Sherbrooke, 2500 boulevard université, Sherbrooke, Québec J1K 2R1, Canada. Guillaume.Marcotte@USherbrooke.ca
authors.forename: Guillaume
authors.initials: G
authors.lastname: Marcotte
authors.forename: Patrick
authors.initials: P
authors.lastname: Ayotte