Hydrogen-Bond Relations for Surface OH Species

Authors: Getachew G. Kebede , Pavlin D. Mitev, Peter Broqvist, Jolla Kullgren , and Kersti Hermansson

This paper concerns thin water films and their hydrogen-bond patterns on ionic surfaces. As far as we are aware, this is the first time H-bond correlations for surface water and hydroxide species are presented in the literature while hydrogen-bond relations in the solid state have been scrutinized for at least five decades. Our data set, which was derived using density functional theory, consists of 116 unique surface OH groups–intact water molecules as well as hydroxides–on MgO(001), CaO(001) and NaCl(001), covering the whole range from strong to weak to no H-bonds. The intact surface water molecules are found to always be redshifted with respect to the gas-phase water OH vibrational frequency, whereas the surface hydroxide groups are either redshifted (OsH) or blueshifted (OHf) compared to the gas-phase OH frequency. The surface H-bond relations are compared with the traditional relations for bulk crystals. We find that the “ν(OH) vs R(H···O)” correlation curve for surface water does not coincide with the solid state curve: it is redshifted by about 200 cm–1 or more. The intact water molecules and hydroxide groups on the ionic surfaces essentially follow the same H-bond correlation curve.

J. Phys. Chem. C2018122 (9), pp 4849–4858
DOI: 10.1021/acs.jpcc.7b10981

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