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Unconventional excited-state dynamics in the concerted benzyl (C7H7) radical self-reaction to anthracene (C14H10)

Author

Listed:
  • Ralf. I. Kaiser

    (University of Hawaii at Manoa)

  • Long Zhao

    (University of Hawaii at Manoa)

  • Wenchao Lu

    (Lawrence Berkeley National Laboratory)

  • Musahid Ahmed

    (Lawrence Berkeley National Laboratory)

  • Vladislav S. Krasnoukhov

    (Samara National Research University)

  • Valeriy N. Azyazov

    (Samara National Research University)

  • Alexander M. Mebel

    (Florida International University)

Abstract

Polycyclic aromatic hydrocarbons (PAHs) are prevalent in deep space and on Earth as products in combustion processes bearing direct relevance to energy efficiency and environmental remediation. Reactions between hydrocarbon radicals in particular have been invoked as critical molecular mass growth processes toward cyclization leading to these PAHs. However, the mechanism of the formation of PAHs through radical – radical reactions are largely elusive. Here, we report on a combined computational and experimental study of the benzyl (C7H7) radical self-reaction to phenanthrene and anthracene (C14H10) through unconventional, isomer-selective excited state dynamics. Whereas phenanthrene formation is initiated via a barrierless recombination of two benzyl radicals on the singlet ground state surface, formation of anthracene commences through an exotic transition state on the excited state triplet surface through cycloaddition. Our findings challenge conventional wisdom that PAH formation via radical-radical reactions solely operates on electronic ground state surfaces and open up a previously overlooked avenue for a more “rapid” synthesis of aromatic, multi-ringed structures via excited state dynamics in the gas phase.

Suggested Citation

  • Ralf. I. Kaiser & Long Zhao & Wenchao Lu & Musahid Ahmed & Vladislav S. Krasnoukhov & Valeriy N. Azyazov & Alexander M. Mebel, 2022. "Unconventional excited-state dynamics in the concerted benzyl (C7H7) radical self-reaction to anthracene (C14H10)," Nature Communications, Nature, vol. 13(1), pages 1-8, December.
    • Handle: RePEc:nat:natcom:v:13:y:2022:i:1:d:10.1038_s41467-022-28466-7
    DOI: 10.1038/s41467-022-28466-7
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    1. Long Zhao & Ralf. I. Kaiser & Wenchao Lu & Bo Xu & Musahid Ahmed & Alexander N. Morozov & Alexander M. Mebel & A. Hasan Howlader & Stanislaw F. Wnuk, 2019. "Molecular mass growth through ring expansion in polycyclic aromatic hydrocarbons via radical–radical reactions," Nature Communications, Nature, vol. 10(1), pages 1-7, December.
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    Cited by:

    1. Guangxian Xu & Hong Wang & Jinyang Zhang & Jiao Gao & Jiwen Guan & Qiang Xu & Donald G. Truhlar & Zhandong Wang, 2024. "Combining synchrotron vacuum-ultraviolet photoionization mass spectrometry and gas chromatography–mass spectrometry for isomer-specific mechanistic analysis with application to the benzyl self-reactio," Nature Communications, Nature, vol. 15(1), pages 1-10, December.

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