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. Pierotti's 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 Pierotti's 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.
Hofinger S., Zerbetto F. (2004). The costly process of creating a cavity in n-octanol. THEORETICAL CHEMISTRY ACCOUNTS, 112, 240-246 [10.1007/s00214-004-0583-2].
The costly process of creating a cavity in n-octanol
ZERBETTO, FRANCESCO
2004
Abstract
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. Pierotti's 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 Pierotti's 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.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
