The evaluation of thermochemical properties of small water clusters (e.g., consisting of 2 - 10 water molecules) is complicated by their dissociative nature. At temperatures for which dissociation of the cluster into molecular fragments has significant probability, an "operational definition" of a cluster is required to restrict the phase space and evaluate a finite value for the partition function or cluster property of interest. We will review a theoretical approach, Dynamical Nucleation Theory (DNT), for evaluating rate constants for cluster evaporation and condensation, which allows for a unique definition of clusters and their thermochemical properties. We will also discuss the relevance of DNT to homogeneous vapor-to-liquid nucleation of water.
Revised: April 16, 2007 |
Published: January 1, 2003
Citation
Garrett B.C., S.M. Kathmann, and G.K. Schenter. 2003.Thermochemistry and kinetics of evaporation and condensation for small water clusters. In Water in Confining Geometries, edited by V. Buch and J. P. Devlin. 25-51. New York, New York:Springer-Verlag.PNNL-SA-35985.