Isolating the Charge-Transfer Component of the Anionic H Bond Via Spin Suppression of the Intracluster Proton Transfer Reaction in the NO~-·H_2O Entrance Channel Complex

摘要

We report the vibrational predissociation spectrum of the NO~-·H_2O complex in the OH stretching region. The ionic H-bonded OH stretch is much less red-shifted and less structured in the vibrational spectrum of NO~-·H_2O than in that of the O_2~-·H_2O cluster, despite the larger proton affinity of NO~- relative to O_2~-. It if argued that the differences between the spectra of these two species are primarily a consequence of the greater charge-transfer character in the O_2~-·H_2O cluster and that the charge-transfer component is much less important in NO~-·H_2O because of its triplet spin character.