Vibrationally induced proton transfer in F- (H2O) and F- (D2O)

Vibrational predissociation spectra of the F(-)(H(2)O) x Ar and F(-)(D(2)O) x Ar complexes are observed over a range of 600 to 3800 cm(-1), which include bands attributed to the fundamentals as well as the first two overtones of the vibrations primarily associated with the shared hydrogen. This information allows us to characterize both the extended potential surface confining the anionic H-bonded hydrogen and the degree to which this motion is coupled to the motions of other atoms in the complex. We analyze these new data with reduced dimensional treatments using explicit potential energy and electric dipole moment surfaces. The often employed one-dimensional treatment with fixed OF distance does not even qualitatively account for the observed isotope dependent level structures, but a simple extension to two dimensions, corresponding to the OF distance and the shared proton position, accurately recovers the observed spectra. The resulting two-dimensional wave functions are used to evaluate the extent of proton transfer in each vibrational level. The main conclusion of this work is that vibrational excitation of the shared proton can be regarded as optically driven, intracluster proton transfer.