How do hydrogen bonds break in small alcohol oligomers?

Recent infrared pump-probe studies on alcohol oligomers in CCl(4) solution reveal that, following OH stretch excitation, ultrafast hydrogen bond (H-bond) breaking takes place on a time scale of 1 ps. To shed light on the mechanism of the H-bond breaking, we consider vibrational predissociation of the H-bonded methanol dimer. We construct a four-dimensional model for the dimer including the H-bond stretch, the donor OH stretch, the donor COH bend, and the OH rotation about the CO axis of the donor. Predissociation rates are calculated with Fermi's golden rule and close coupling approaches. Our results indicate that the predissociation leads to products with highly excited OH rotations. The predissociation rates strongly depend on the hydrogen bond strength. From our results, a simple nonadiabatic curve crossing picture for the predissociation process emerges, which provides a framework for future studies of solvent-assisted vibrational predissociation.