IR and Raman spectra of liquid water: Theory and interpretation

IR and Raman (parallel- and perpendicular-polarized) spectra in the OH stretch region for liquid water were measured some years ago, but their interpretation is still controversial. In part, this is because theoretical calculation of such spectra for a neat liquid presents a formidable challenge due to the coupling between vibrational chromophores and the effects of motional narrowing. Recently we proposed an electronic structure/molecular dynamics method for calculating spectra of dilute HOD in liquid D(2)O, which relied on ab initio calculations on clusters to provide a map from nuclear coordinates of the molecules in the liquid to OH stretch frequencies, transition dipoles, and polarizabilities. Here we…

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  National Science Foundation