15min:
IR SPECTROSCOPY OF [Ag cdot(CO2)n]- CLUSTERS: IMPLICATIONS FOR REDUCTIVE ACTIVATION OF CO2.

BENJAMIN J. KNURR AND J. MATHIAS WEBER, JILA and Department of Chemistry and Biochemistry, University of Colorado, Boulder, CO 80309.

Reduction of CO2 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 CO2 molecule, which could be a significant step towards CO2 recycling. However there is still much uncertainty in the role of solvent effects on these chemical processes. We present infrared spectra of [Ag cdot(CO2)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 CO2 in the presence of a Ag anion. The structures of the [Ag cdot(CO2)n]- clusters are discussed in the framework of density functional theory. We compare and contrast the findings of [Ag cdot(CO2)n]- to those recently published on [Au cdot(CO2)n]- [1].

\noindent 1. B.J. Knurr and J.M. Weber, J. Amer. Chem. Soc., 134 (2012) 18804-18808.