Geometrical H/D isotope effect on hydrogen bonds in charged water clusters

To investigate the proton/deuteron geometrical isotope effect of positively and negatively charged water complexes, H5O2+ and H3O2-, we have carried out accurate ab initio path integral simulations considering the electron correlation effect. It has been found that the isotope effect on the hydrogen bond is different between these two species in that the oxygen separation becomes shorter in H5O2+ while longer in H3O2- by deuteron substitution. This behavior is ascribed to the change in the quantum effect of hydrogen bonds whether the shared hydrogen is on a single or double well potential surface. Copyright © 2005 American Chemical Society.