Abstract
An expression is derived for the electrostatic energy of an array of charged, polarizable atoms representing a solute molecule in a cavity in a dielectric continuum, using a generalization of the theory of the reaction field. Explicit formulas are obtained for the case of a spherical cavity. The formulas are used to calculate Gibbs energies and entropies of proton transfer between carboxylic acids in water, using atom polarizabilities from previous studies and atom charges on the COOH and COO− groups which are optimzed to fit experimental Gibbs energies of proton transfer between acyclic carboxylic acids involving monovalent anions. A cavity radius increment is likewise optimized. The optimized fit is good, and the parameters are reasonably consistent with data from other sources (charges from molecular orbital theory, experimental dipole moments, and partial molal volumes). Calculations for reactions involving divalent anions or bicyclo[2.2.2]octane‐1‐carboxylic acids yield correct Gibbs energies with th...
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