PNNL

Abstract

We report experimental and computational results pertaining to the activation of single water molecules by single, atomic Group 10 metal anions. The anion photoelectron spectra of [Pt(H2O)]-, [Ni(H2O)]-, and [Pd(H2O)]- exhibit spectral features that are due both to anion-molecule complexes of the form, M-(H2O), where M = Pt, Ni, Pd, and to the formation of HMOH- intermediates. Computations at the CCSD(T) level of theory provide structures and vertical detachment energies of both HMOH- and H2MO- intermediates. The calculated vertical detachment energies for HMOH- are in good agreement with the photoelectron spectra and thus supports their identification. The formation of HMOH- intermediates requires that one O-H bond in water be broken; the presence of these species shows that water has been activated. The formation of H2MO- intermediates, however, requires that two O-H bonds be broken. While the photoelectron spectra do not exhibit features that can unambiguously be assigned to H2MO-, the observation of PtO- suggests the presence of H2PtO-.