Understanding the intrinsic properties of the hydrated carbon dioxide radical anions CO
2.−(H
2O)
n is relevant for electrochemical carbon dioxide functionalization. CO
2.−(H
2O)
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 CO
2.− with the hydrogen-bonding network.
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