PRECURSOR OF THE I-AQ(-) CHARGE-TRANSFER-TO-SOLVENT (CTTS) BAND IN I-CENTER-DOT(H2O)(N) CLUSTERS

Ultraviolet charge-transfer-to-solvent (CTTS) bands are general spectr al features of inorganic salts dissolved in dipolar (e.g., aqueous) so lvents. The bands originate from excitations of the anions, and the ex cited states are thought to involve a delocalized electronic state sup ported by the arrangement of solvent molecules around the ion in the g round state. These diffuse states have fascinated physical chemists si nce the 1930s, who first used continuum models to explain the phenomen on and then later refined the treatment to include local molecular int eractions. In this paper, we report that CTTS bands evolve from featur es present in very small gas phase clusters, I- (H2O)(n), n = 1-4, and discuss how localization of the continuum wave function of the ejecte d electron acts as a precursor to the bound excited State in the liqui d. (C) 1996 American Institute of Physics.