ELECTRON-TRANSFER REACTIONS IN CLUSTERS - THE EFFECT OF POLAR-SOLVENTS ON THE (2P3S) RYDBERG STATE OF AZABICYCLO-OCTANE

(1+1) mass resolved excitation spectra are reported for the (2p3s)<--( 2p)(2) Rydberg transition of azabicyclooctane (ABCO) van der Waals clu sters. The solvent molecules employed in this study are mostly polar. The polar solvent cluster spectra are red shifted from those of the ba re molecule ABCO by more than 500 cm(-1) in most cases. This large inc rease in the interaction energy of the ABCO molecule Rydberg state in polar solvent clusters with respect to that of the ground state ABCO c luster is due to an exchange delocalization or electron transfer inter action for the excited state cluster. The ABCO Rydberg state electron is delocalized into the available (virtual) orbitals of the polar solv ent molecule. Relaxation dynamics are measured for the generation of t he electron transfer state of the cluster. This behavior is similar to that characterized for other cyclic amines in polar solvent clusters. (C) 1996 American Institute of Physics.