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

ABSTRACT: Fourier transform infrared spectroscopy of laser-irradiated cryogenic crystals shows that vibrational excitation of CO leads to the production of equal amounts of CO₂ and C₃O₂. 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(³P) + CO₂. C(³P) then undergoes barrierless recombination with two other CO molecules forming C₃O₂. 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. Th

SUBMITTER: DeVine JA 

PROVIDER: S-EPMC9014413 | biostudies-literature | 2022 Apr

REPOSITORIES: biostudies-literature