A conformational analysis of propylene carbonate molecules adsorbed at the mercury electrode

A programme has been conceived which applies to conformation analysis of propylene carbonate molecules adsorbed at the Hg electrode. Several molecular orientations are selected in order to fix the atoms, bearing point charges, in the configuration space. Calculations are performed with semi-empirical functions representing the energy terms of molecular clusters. Atom-atom and point-charge-point-charge interactions are used to determine the van der Waals interaction between adsorbed molecules. Dispersion components of the atom-metal phase interaction and self-image interactions of point charges yield the metal phase-adsorbed molecule van der Waals interaction. The effects of the internal molecular degrees of freedom and of the external electric field upon the molecular point dipole have been taken into account. The ensemble distribution function, computed within the limits of doublet interaction leads to the evaluation of the average dipole moment and the inner-layer capacity. This theoretical value is compared to the experimental inner-layer capacitance measured in the propylene carbonate solvent-Hg electrode system. © 1983 Elsevier Sequoia S.A.