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A single molecule as a dielectric medium.

For three molecules with weak or negligible charge overlap, we prove that the three-body interaction energy obtained from quantum perturbation theory (to leading order) fits a dielectric model with a nonlocal electronic screening function. The electronic charge cloud of each molecule acts as a dielectric medium for the interaction of the remaining two with the nonlocal dielectric function epsilon(r,r') obtained by O. S. Jenkins and K. L. C. Hunt [J. Chem. Phys. 119, 8250 (2003)], by considering the charge redistribution induced in a single molecule by an external perturbation. The dielectric function depends parametrically on the coordinates of the nuclei, within the Born-Oppenheimer approximation. We also prove that the force on each nucleus in molecule A depends on intramolecular dielectric screening within A. The potential from the charge distribution of B, screened by C acting as a dielectric medium, is further screened linearly within A; and similarly, with the roles of B and C reversed. In addition, the potential due to the unperturbed charge distribution of B and the potential due to the unperturbed charge distribution of C, acting simultaneously, are screened nonlinearly within A. The results show that nonlocal dielectric theory holds on the molecular level, provided that the overlap of the electronic charge distributions is weak.