title: Charge transfer and OH vibrational frequency red shifts in nitrate-water clusters.
abstract: A theoretical study of charge transfer (CT) characteristics in nitrate (NO3(-)) anion-water complexes is presented, together with those for the halides, F-, Cl-, and Br-, for comparison. The relation between the vibrational frequency red shifts of the hydrogen (H)-bonded OH stretches and CT from the anion to the water molecule, established in previous work for the one-water complexes of the halides, is studied for both the one- and six-water nitrate complexes and is extended to the six-water case for the halides. In NO3(-) x H2O, the water molecule receives about as much charge as that in Br- x H2O. In a result consistent with aqueous phase infrared experiments [Bergström, P. A.; Lindgren, J.; Kristiansson, O. J. Phys. Chem. 1991, 95, 8575-8580], the CT and OH red shift in NO3(-) x 6 H2O are found to be smaller than those for all of the six-water halide complexes, despite the presence of three H-bonding sites. The inability of the nitrate anion to effect substantial CT lies in the preservation of the pi-system being energetically favored over charge localization and enhancement of the strengths of the multiple H-bonds.
authors: Département de Chimie, UMR 8640 PASTEUR, Ecole Normale Supérieure, 24 rue Lhomond, 75231 Paris Cedex 05, France. ramesh@chimie.ens.fr
authors: Sai G
authors: SG
authors: Ramesh
authors: Suyong
authors: S
authors: Re
authors: James T
authors: JT
authors: Hynes