Carbon Trioxide: Its Production, Infrared Spectrum, and Structure Studied in a Matrix of Solid CO2

Reactions of oxygen atoms with CO2 molecules to give a species identified as CO3 have been observed in three systems: (1) the photolysis of solid CO2 at 77°K with vacuum‐ultraviolet light from a xenon resonance lamp; (2) the photolysis of O3 in a CO2 matrix at 50°—60°K with 2537‐A light from a mercury arc; and (3) the radio‐frequency discharge of CO2 gas followed by trapping of products at 50°—70°K. The infrared spectrum of the species includes absorptions at 568, 593, 972, 1073, 1880, 2045, 3105, and 3922 cm−1. Isotopic studies using CO2 enriched with 18O or 13C show that the molecular formula is CO3 and provide a basis for determining the molecular structure. Frequency assignments and isotopic product‐rule calculations favor a planar C2v molecule in which the carbon atom is bonded to the unique oxygen atom by a strong carbonyl bond and to two equivalent oxygen atoms by weaker bonds. There is presumably covalent bonding between the two equivalent oxygen atoms. In the proposed frequency assignment it is a...

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