Journal of Chemical Physics, Vol.111, No.11, 5081-5090, 1999
Hydrogen bond network fluctuations in small (H2O)(n) clusters (n=8-12-24)
Molecular dynamic studies of three (H2O)(n) clusters (n=8-12-24) were performed using our recently developed many-body model TCPE [J. Chem. Phys. 107, 9105 (1997)] in the microcanonical ensemble. The trajectories were analyzed using a new structural local index derived from one of the many-body energetic term of TCPE. In the energy domain where the clusters are in a liquidlike state, a dynamical equilibrium is theoretically predicted to exist among molecules in the PHB1 and the PHB2 state (i.e., among molecules which one of their protons is involved in one hydrogen bond, the PHB1 state, and molecules which both of their protons are involved in two hydrogen bonds, the PHB2 state). The enthalpy and entropy changes corresponding to that equilibrium for the three clusters range from 0.75 to 1.10 kcal mol(-1) and from -7 to -3.8 cal mol(-1) K-1. Such an equilibrium between two species of hydrogen bonded molecules could be related to that experimentally observed in the case of liquid water at ambient conditions. In particular, the entropy changes corresponding to PHB2/PHB1 equilibrium in the case of the three clusters are very close to those experimentally reported for liquid water (about 6.6 +/- 0.5 cal mol(-1) K-1), suggesting that the equilibrium observed in the case of liquid water could correspond to a PHB2/PHB1 equilibrium. The analysis of hydrogen bond networks in terms of PHBm states appears thus to be an encouraging way in characterising the dynamical properties of water systems.