title: Vibrational spectroscopy of small hydrated CuOH+ clusters.
abstract: Coordinated copper hydroxide centers can play an important role in copper catalyzed water oxidation reactions. To have a better understanding of the interactions involved in these complexes, we studied the vibrational spectra of D2 tagged CuOH(+)(H2O)n clusters in the OH stretch region. These clusters are generated by electrospray ionization and probed via cryogenic ion vibrational spectroscopy. The results show that the copper center in the n = 3 clusters has a distorted square planar geometry. The coordination in CuOH(+)(H2O)n is therefore more akin to Cu(2+)(H2O)n with four ligands in the first solvation shell than Cu(+)(H2O)n with two ligands in the first solvation shell. There is also no evidence of any strong axial ligand interactions. The well-resolved experimental spectra enabled us to point out some discrepancies in the calculated spectra, which were found to be highly dependent on the level of theory used.
authors.affiliation: Department of Chemistry, University of Wisconsin , 1101 University Avenue, Madison, Wisconsin 53706, United States.
authors.forename: Brett M
authors.initials: BM
authors.lastname: Marsh
authors.forename: Jia
authors.initials: J
authors.lastname: Zhou
authors.forename: Etienne
authors.initials: E
authors.lastname: Garand