Exploring the Origins of Spectral Signatures of Strong Hydrogen Bonding in Protonated Water Clusters.

ABSTRACT

The effects of anharmonicity on the spectral features of strong ionic hydrogen bonds are explored through reduced dimensional studies of the couplings between the hydrogen bonding OH and the donor-acceptor OO stretching vibrations in protonated water clusters with 2-4 water molecules. Specifically, this study focuses on how the anharmonicities and couplings in these ions are reflected in the vibrational spectra by exploring the intensities of the transitions to states with excitation in both the OH and the OO stretching vibrations and changes in the frequency of the OO stretching vibration when the OH stretching vibration is excited. These questions are addressed through the application of several approximate treatments that are based on an adiabatic separation of the high-frequency OH and low-frequency OO stretching vibrations as well as low-order expansions of the potential and dipole surfaces. While an adiabatic approximation captures most of the trends found in the spectra and from an analysis of the two-dimensional model, a vibrational Franck-Condon approach fails to capture the intensities of these transitions. Of the terms in the expansion of the dipole moment function, those that are proportional to ΔrOH and ΔrOH2 are found to provide the largest contributions to the calculated intensities of the transitions involving excitation of both the OH and the OO stretches. This leads to the conclusion that the intensities of these transitions encode information about the frequency and anharmonicity of the OH stretching vibration and how they are affected by changes in the OO distance. The anharmonicity of the potential also leads to changes in the OO stretching frequency with excitation of the OH stretching vibration. The direction of this change in frequency encodes additional information about the strength of the ionic hydrogen bond.