Abstract
We report a study of the rōle of repulsive intermolecular forces in chiral discrimination. A realistic model based on hard-core repulsive potentials, the RISM formalism, and a superposition approximation is used to compare the interaction between the same (dextro—dextro) and opposite (dextro—laevo) enantiomers of chlorofluoroacetonitrile in the liquid phase, at room temperature. Chiral discrimination arises through differences in pairwise packing in the two types of pair. Calculations are made also for the gas phase. The excess volume of mixing (−0.1 to −0.2 cm 3 mol 1̄), derived predominantly from nearest-neighbour contact distances, shows more efficent (d, l) contact packing. The excess enthalpy ( = 12 J mol −1, obtained by using an isotropic Lennard-Jones interaction, weights larger intermolecular distances and is endothermic. These results emphasize the need to consider the dependence of intermolecular orientational correlations on intermolecular separation in the interpretation of experimental data on chiral discrimination in liquids. Experimental results are not available for the system studied here, however the results are compatible with measured values for other systems.
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