Journal of Chemical Physics, Vol.104, No.8, 2891-2897, 1996
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 clusters. The solvent molecules employed in this study are mostly polar. The polar solvent cluster spectra are red shifted from those of the bare molecule ABCO by more than 500 cm(-1) in most cases. This large increase in the interaction energy of the ABCO molecule Rydberg state in polar solvent clusters with respect to that of the ground state ABCO cluster is due to an exchange delocalization or electron transfer interaction for the excited state cluster. The ABCO Rydberg state electron is delocalized into the available (virtual) orbitals of the polar solvent molecule. Relaxation dynamics are measured for the generation of the electron transfer state of the cluster. This behavior is similar to that characterized for other cyclic amines in polar solvent clusters.
Keywords:NONPOLAR-SOLVENTS;SOLVATION