VAN-DER-WAALS INTERACTION BETWEEN A MOLECULE AND A SPHERICAL CAVITY IN A METAL - NONLOCALITY AND ANISOTROPY EFFECTS

The electric response field of a small spherical metallic cavity to a molecule characterized by fluctuating dipolar and quadrupolar moments is built from spherical tensor theory. The electric susceptibility of the field gradient between the two points inside the metallic cavity i s formulated by a general expression of the van der Waals energy betwe en the two partners. The induction contribution is introduced by using the field gradient susceptibilities of the cavity at zero frequency. In order to illustrate the nonlocal effects as well as the importance of the curvature of the metallic cavity on the magnitude of the physis orption energy, we present numerical results for typical systems (HF, HCl on Ag, Al, and Cu).