title: Ligand influence on the electronic spectra of monocationic copper-bipyridine complexes.
abstract: We present photodissociation spectroscopy and computational analysis of three monocationic Cu-bipyridine complexes with one additional ligand of different interaction strength (N2, H2O and Cl) in the visible and UV. All three complexes show similar ππ* bands with origins slightly above 4 eV and vibrational band contours that are due to bipyridine ring deformation modes. Experiments at low temperature show that excited-state lifetime is the limiting factor for the width of the vibrational features. In the case of Cl as a ligand, there is a lower lying bright ligand-to-ligand charge-transfer state around 2.75 eV. The assignment of the transitions was made based on equation-of-motion coupled-cluster calculations. While the nature of the ligand does not significantly change the position of the bright ππ* state, it drastically changes the excited-state dynamics.
authors.affiliation: JILA and Department of Physics, University of Colorado, Boulder, CO 80309-0440, USA.
authors.forename: Shuang
authors.initials: S
authors.lastname: Xu
authors.affiliation: Department of Chemistry, University of Southern California, Los Angeles, CA 90089-0482, USA.
authors.forename: Samer
authors.initials: S
authors.lastname: Gozem
authors.affiliation: Department of Chemistry, University of Southern California, Los Angeles, CA 90089-0482, USA.
authors.forename: Anna I
authors.initials: AI
authors.lastname: Krylov
authors.affiliation: JILA and Department of Chemistry and Biochemistry, University of Colorado, Boulder, CO 80309-0440, USA. weberjm@jila.colorado.edu.
authors.forename: Casey R
authors.initials: CR
authors.lastname: Christopher
authors.affiliation: JILA and Department of Chemistry and Biochemistry, University of Colorado, Boulder, CO 80309-0440, USA. weberjm@jila.colorado.edu.
authors.forename: J Mathias
authors.initials: JM
authors.lastname: Weber