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

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 resonanc...

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Bibliographic Details
Published in:Chemistry : a European journal 2019-08, Vol.25 (43), p.10165-10171
Main Authors: Herburger, Andreas, Ončák, Milan, Siu, Chi‐Kit, Demissie, Ephrem G., Heller, Jakob, Tang, Wai Kit, Beyer, Martin K.
Format: Article
Language:English
Subjects:
ab initio calculations
Absorption spectra
Anions
Bend strength
Carbon dioxide
carbon dioxide radical anions
Chemistry
clusters
Cyclotron resonance
Electrochemistry
Infrared spectroscopy
Ions
Libration
mass spectrometry
Organic chemistry
Quantum chemistry
Spectroscopy
Spectrum analysis
Vibration
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Summary: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. All action: Understanding the intrinsic properties of the hydrated carbon dioxide radical anions CO2.−(H2O)n is relevant for electrochemical carbon dioxide functionalization. Thus, CO2.−(H2O)n (n=2–61) is investigated by using infrared action spectroscopy in the 1150–2220 cm−1 region in an ion cyclotron resonance cell cooled to T=80 K.
ISSN:0947-6539
1521-3765
DOI:10.1002/chem.201901650