VIBRATIONAL PREDISSOCIATION IN HYDROGEN-BONDED OH...O COMPLEXES VIA OH STRETCH OO STRETCH ENERGY-TRANSFER

A theory for vibrational predissociation of hydrogen-bonded OH...0 complexes via OH stretch-00 stretch energy transfer is constructed, motivated by a recent experiment on vibrational predissociation of hydrogen-bonded ethanol dimer in solution. The theory employs a vibrationally adiabatic perspective, exploiting the frequency separation between the OH and OO stretches. The nonadiabatic coupling responsible for the hydrogen bond rupture subsequent to OH stretch excitation is found analytically. A lifetime for ethanol dimer of almost-equal-to 10 ps is estimated, which is within a factor of two of the experimental result. General trends are predicted and discussed for other OH...O complexes.