A hydrogen-bonded complex of OH with CO is identified along the reaction coordinate for the OH+CO↔HOCO→H+CO2 reaction. The existence of this linear OH–CO complex is established by infrared action spectroscopy, which accesses vibrational stretching and bending modes of the complex. Complementary electronic structure calculations characterize the OH–CO and OH–OC complexes, the transition state for HOCO formation, and the reaction pathways that connect these complexes directly to the HOCO intermediate.

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