Science, Vol.275, No.5301, 817-820, 1997
On the Quantum Nature of the Shared Proton in Hydrogen-Bonds
The relative influence of thermal and quantum fluctuations on the proton transfer properties of the charged water complexes H5O2+ and H3O2- was investigated with the use of 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 H5O2+ behaved in an essentially classical manner, whereas in the H3O2- low-barrier hydrogen bond, quantum zero-point motion played 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.
Keywords:MOLECULAR-DYNAMICS SIMULATION;DENSITY-FUNCTIONAL THEORY;ENZYME CATALYSIS;WATER CLUSTERS;THERMAL CONDITIONS;HYDROXIDE ION;SPECTROSCOPY;HYDRONIUM;SOLVATION;SYSTEMS