Abstract

Van der Waals complexes are loosely bound clusters of atoms or molecules which can be made conveniently by free jet expansions of pure or mixed vapors through a supersonic nozzle. Although these complexes are bound only by 0-0.2 eV, they have unique geometries that can be determined by techniques such as microwave spectroscopy (1). These species are of considerable interest not simply from the perspectives of molecular structure and thermodynamics, but more so because they are, for chemically reactive pairs, frozen collision complexes which can be isolated long enough to permit inspection of features such as stepwise solvent effects, energy transfer in oriented reactants, induction of chemical reactions, preparation of cationic reaction intermediates, and nonstatistical effects in unimolecular decomposition of ionic complexes.

© 1988 Optical Society of America