Ab initio calculation of molar volumes: Comparison with experiment and use in solvation models

A simple and efficient procedure of calculating molecular volume (VM) based on the Monte Carlo method is presented. The volume of a molecule is defined by the volume occupied by the 0.001‐au electron density envelope. We have employed this method to compute the molecular volumes (VM) of a large selection of organic molecules and compare them with the corresponding molar volumes (Vm) measured in the liquid state. A strong correlation is found to exist between the VM and Vm values (VM/Vm ≈ 0.75). Using this linear relationship, the calculated molecular volume may provide an estimate of the cavity‐volume parameter in solvent‐effect calculations. As a chemical application of molecular volume, we have investigated the conformational equilibrium of 1,2‐difluoroethane in the liquid state using the self‐consistent reaction field theory. © 1995 by John Wiley & Sons, Inc.

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