Spin-Forbidden Carbon–Carbon Bond Formation in Vibrationally Excited α-CO

[Image: see text] Fourier transform infrared spectroscopy of laser-irradiated cryogenic crystals shows that vibrational excitation of CO leads to the production of equal amounts of CO(2) and C(3)O(2). The reaction mechanism is explored using electronic structure calculations, demonstrating that the lowest-energy pathway involves a spin-forbidden reaction of (CO)(2) yielding C((3)P) + CO(2). C((3)P) then undergoes barrierless recombination with two other CO molecules forming C(3)O(2). Calculated intersystem crossing rates support the spin-forbidden mechanism, showing subpicosecond spin-flipping time scales for a (CO)(2) geometry that is energetically consistent with states accessed through vibrational energy pooling. This spin-flip occurs with an estimated ∼4% efficiency; on the singlet surface, (CO)(2) reconverts back to CO monomers, releasing heat which induces CO desorption. The discovery that vibrational excitation of condensed-phase CO leads to spin-forbidden C–C bond formation may be important to the development of accurate models of interstellar chemistry.