When a Ne:CO=100 mixture is codeposited at approximately 5 K with a beam of neon atoms that have been excited in a microwave discharge, several new infrared absorptions appear in the resulting sample deposit. Detailed isotopic substitution experiments support the assignment of these absorptions to CO+, trans‐OCCO+, and trans‐OCCO. Analysis of the infrared data has permitted determination of the CO‐stretching force constants of the dimer cation and anion and has yielded a preliminary estimate of the valence angles for trans‐OCCO. The role of electron capture in the ‘‘photobleaching’’ of trans‐OCCO+ by visible radiation is considered.

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