The costly process of creating a cavity in n-octanol

Free-energy perturbation calculations are used to evaluate the free energy of cavity formation in n-octanol. A detailed theoretical analysis of the procedure is given and some limiting value phenomena are discussed. The data become subject to a three-parameter fit and a revised formulation of the popular approach due to Pierotti of calculating cavitation free energies is given. Pierottis approach is based on the equation derived from scaled particle theory (SPT) by Reiss et al. [(2000) J. Chem. Phys. 31:369–380]. The revision of Pierottis approach has the important advantage of being completely independent of the solvent hard-sphere radius, an empirical parameter in the standard procedure, which is hard to define in a uniformly valid way.Acknowledgments. S.H. gratefully acknowledges supercomputing support from the University of Linz, GUP, Professor Volkert and Dr. Kranzlmüller, and the University of Salzburg, RIST⁺⁺, Professor Zinterhof.Proceedings of the 11th International Congress of Quantum Chemistry satellite meeting in honor of Jean-Louis Rivail