title: Signatures of Size-Dependent Structural Patterns in Hydrated Copper(I) Clusters, Cu+(H2O)n=1-10.
abstract: The isomers of a hydrated Cu(I) ion with n = 1-10 water molecules were investigated by using ab initio quantum chemistry and an automated isomer-search algorithm. The electronic structure and vibrational spectra of the hundreds of resulting isomers were used to analyze the source of the observed bonding patterns. A structural evolution from dominantly two-coordinate structures (n = 1-4) toward a mixture of two- and three-coordinate structures was observed at n = 5-6, where the stability provided by expanded hydrogen-bonding was competitive with the dominantly electrostatic interaction between the water ligand and remaining binding sites of the metal ion. Further hydration (n = 7-10) led to a mixture of three- and four-coordinate structures. The metal ion was found, through spectroscopic signatures, to appreciably perturb the O-H bonds of even third-shell water molecules, which highlighted the ability of this nominally simple ion to partially activate the surrounding water network.
authors.affiliation: Department of Chemistry, University of Utah , 315 South 1400 East, Salt Lake City, Utah 84112, United States and.|Henry Eyring Center for Theoretical Chemistry, University of Utah , 315 South 1400 East, Salt Lake City, Utah 84112, United States.
authors.forename: Jonathan D
authors.initials: JD
authors.lastname: Herr
authors.affiliation: Department of Chemistry, University of Utah , 315 South 1400 East, Salt Lake City, Utah 84112, United States and.|Henry Eyring Center for Theoretical Chemistry, University of Utah , 315 South 1400 East, Salt Lake City, Utah 84112, United States.
authors.forename: Ryan P
authors.identifier: http://orcid.org/0000-0002-3292-9805
authors.initials: RP
authors.lastname: Steele