LIQUID-STATE QUANTUM-CHEMISTRY - AN IMPROVED CAVITY MODEL

We develop a very general computational scheme allowing all the physic al contributions to the solute-solvent interaction in the quantum chem ical study of a solvated molecule to be taken into account. This schem e is based upon a model in which the solvent is assimilated to a conti nuum and the solute placed in a cavity of any shape. This approach tak es advantage of the facilities offered by the reaction field factors f ormalism, which generalizes a model introduced by Kirkwood. Applied to the study of the liquid state structure of formamide and acetamide an d to the solvent effects on the barrier to internal rotation in these molecules this method appears to be quite efficient. It offers a large number of possible applications to problems of chemical interest.