HCl Hydrates as Model Systems for Protonated Water

• Published in: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Molecules, spectroscopy, kinetics, environment, & general theory, 2008-03, Vol.112 (11), p.2144-2161
• Main Authors: Buch, V, Dubrovskiy, A, Mohamed, F, Parrinello, M, Sadlej, J, Hammerich, A. D, Devlin, J. P
• Format: Article
• Language: English
• ISSN: 1089-5639; 1520-5215
• DOI: 10.1021/jp076391m

Ab initio molecular dynamics simulations are presented of vibrational dynamics and spectra of crystal HCl hydrates. Depending on the composition, the hydrates include distinct protonated water forms, which in their equilibrium structures approximate either the Eigen ion H3O+(H2O)3 (in the hexahydrate) or the Zundel H2O···H+···OH2 ion (in the di- and trihydrate). Thus, the hydrates offer the opportunity to study spectra and dynamics of distinct species of protonated water trapped in a semirigid solvating environment. The experimentally measured spectra are reproduced quite well by BLYP/DZVP-level calculations employing Fourier transform of the system dipole. The large overall width (800−1000 cm-1) of structured proton bands reflects a broad range of solvating environments generated by crystal vibrations. The aqueous HCl solution was also examined in search of an objective criterion for separating the contributions of “Zundel-like” and “Eigen-like” protonated forms. It is suggested that no such criterion exists since distributions of proton-related structural properties appear continuous and unimodal. Dipole derivatives with respect to OH and O···H+ stretches in water and protonated water were also investigated to advance the understanding of the corresponding IR intensities. The effects of H bonding and solvation on the intensities were analyzed with the help of the Wannier centers' representation of electron density.