Infrared Spectroscopy of Size-Selected Hydrated Carbon Dioxide Radical Anions CO2.−(H2O)n (n=2–61) in the C−O Stretch Region

Abstract

Understanding the intrinsic properties of the hydrated carbon dioxide radical anions CO2.−(H2O)n is relevant for electrochemical carbon dioxide functionalization. CO2.−(H2O)n (n=2–61) is investigated by using infrared action spectroscopy in the 1150–2220 cm−1 region in an ICR (ion cyclotron resonance) cell cooled to T=80 K. The spectra show an absorption band around 1280 cm−1, which is assigned to the symmetric C−O stretching vibration νs. It blueshifts with increasing cluster size, reaching the bulk value, within the experimental linewidth, for n=20. The antisymmetric C−O vibration νas is strongly coupled with the water bending mode ν2, causing a broad feature at approximately 1650 cm−1. For larger clusters, an additional broad and weak band appears above 1900 cm−1 similar to bulk water, which is assigned to a combination band of water bending and libration modes. Quantum chemical calculations provide insight into the interaction of CO2.− with the hydrogen-bonding network.