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  Spin-forbidden carbon–carbon bond formation in vibrationally excited α-CO

DeVine, J., Choudhury, A., Lau, J. A., Schwarzer, D., & Wodtke, A. M. (2022). Spin-forbidden carbon–carbon bond formation in vibrationally excited α-CO. The Journal of Physical Chemistry A, 126(14), 2270-2277. doi:10.1021/acs.jpca.2c01168.

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 Creators:
DeVine, J.1, Author           
Choudhury, A.1, Author           
Lau, J. A.1, Author           
Schwarzer, D.1, Author           
Wodtke, A. M.1, Author           
Affiliations:
1Department of Dynamics at Surfaces, Max Planck Institute for Multidisciplinary Sciences, Max Planck Society, ou_3350158              

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Free keywords: Infrared spectroscopy, vibrational excitation
 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. 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.

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Language(s): eng - English
 Dates: 2022-03-232022-02-172022-04-052022-04-14
 Publication Status: Published in print
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 Rev. Type: Peer
 Identifiers: DOI: 10.1021/acs.jpca.2c01168
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Funding program : Open Access Funding
Funding organization : Max Planck Society

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Title: The Journal of Physical Chemistry A
Source Genre: Journal
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Pages: - Volume / Issue: 126 (14) Sequence Number: - Start / End Page: 2270 - 2277 Identifier: ISSN: 1089-5639
ISSN: 1520-5215