Can the pH value of water solutions be estimated by quantum chemical calculations of small water clusters?

In the study, various water clusters were explored from the point of view of the proton transfer between H-bonded neighbors. A relatively modest approach-the MP2/6-31++G(d,p) level-was chosen as acceptable considering the fact that also larger systems have to be included. The tight ion-pair model (with usually three fixed O-O distances) was adopted for the autodissociation process. First, cluster-estimated pH values rapidly decrease as cluster size increases from 2 to 6. For larger clusters in gas phase, the topology of H bonds plays an important role, varying pH from 7 to 13 in hexamers and from 5 to 15 in octamer clusters. The relationship energy/distance was quantified, too. Enhancing our model with the conductorlike screening model (COSMO) approach brought significant improvement in description of the autodissociation reaction with a stable zwitterionic structure. However, when the O-O restrictions were released, the small barrier for backward reaction disappeared, reforming neutral cluster spontaneously. Also Boltzmann weighting procedure was applied, and for the explored clusters in vacuo, the series of pH 25-18-14-13-10 was obtained for cluster sizes n=2, 3, 4, 6, 8. Using the COSMO approach, the analogous series is 15-14-12-10-9. The limit of the series is still about two to three units above the experimentally known pH. In order to reach the size-independent (bulk) value, larger clusters are needed. However, the situation is far from hopeless since (as it was proven in the study) four-coordinated molecules are not involved in the proton transfer process directly; they can only be a part of the surrounding environment. (c) 2006 American Institute of Physics.