IR SPECTROSCOPY OF [Ag$\cdot$(CO$_{2}$)$_{n}$]$^{-}$ CLUSTERS: IMPLICATIONS FOR REDUCTIVE ACTIVATION OF CO$_{2}$

Author Institution: JILA and Department of Chemistry and Biochemistry, University of Colorado, Boulder, CO 80309Reduction of CO$_{2}$ is an essential step in its chemical conversion from a greenhouse gas to useable fuel stocks, but is energetically unfavorable. Association with anions has been shown to facilitate partial charge transfer to a target CO$_{2}$ molecule, which could be a significant step towards CO$_{2}$ recycling. However there is still much uncertainty in the role of solvent effects on these chemical processes. We present infrared spectra of [Ag$\cdot$(CO$_{2}$)$_{n}$]$^{-}$ ($n = 2 - 11$) to elucidate the nature of the charge carrier in the cluster, the effects of solvation on the charge distribution and the amount of reductive activation of CO$_{2}$ in the presence of a Ag anion. The structures of the [Ag$\cdot$(CO$_{2}$)$_{n}$]$^{-}$ clusters are discussed in the framework of density functional theory. We compare and contrast the findings of [Ag$\cdot$(CO$_{2}$)$_{n}$]$^{-}$ to those recently published on [Au$\cdot$(CO$_{2}$)$_{n}$]$^{-}$ [1]. 1. B.J. Knurr and J.M. Weber, J. Amer. Chem. Soc., 134 (2012) 18804-18808