Science Abstract

Abstract


The relative influence of thermal and quantum fluctuations on the proton transfer properties of the charged water complexes H5O 2+ and H3O 2- was investigated using ab initio techniques. These small systems can be considered as prototypical representatives of strong and intermediate strength hydrogen bonds. The shared proton in the strongly hydrogen bonded H5O 2+ was found to behave in an essentially classical manner, whereas in the H3O - low--barrier hydrogen bond, quantum zero--point motion was found to play a crucial role even at room temperature. This behavior can be traced back to a small difference in the oxygen--oxygen separation, and hence to the strength of the hydrogen bond.