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<p>Roaming-mediated isomerization is a universal reaction mechanism in photochemistry, yet solvent-dependent pathways of roaming intermediates remain poorly understood, particularly for environmentally relevant halogen compounds involved in ozone depletion. Here, using femtosecond time-resolved X-ray solution scattering, we resolve the solvent-dependent roaming dynamics of CHBr<sub>3</sub> in methanol and methylcyclohexane. By combining multi-method experimental analysis, machine learning-assisted ab initio molecular dynamics simulations, and density functional theory calculations, we uncover distinct solvent-steered reaction pathways. In methanol, roaming enhances solute-solvent interactions, leading to solvolysis before a stable isomer forms. In methylcyclohexane, roaming facilitates isomerization to a long-lived iso-CHBr<sub>2</sub>-Br product. Direct dissociation into CHBr<sub>2</sub> + Br competes with both pathways in either solvent. By tracking bond-length oscillations and angular dynamics in real time, we visualize how the condensed-phase environment governs the branching ratio between competing pathways. Our findings establish solute-solvent interactions as key factors controlling roaming-mediated reactions in CHBr<sub>3</sub>, with broad implications for photochemical outcomes in solution.</p>

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Ultrafast solvent-modulated roaming mechanism in bromoform revealed by femtosecond X-ray solution scattering

  • 期刊论文

  • 出版模式：

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  • 发表日期：

    2026年2月9日

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  • Peiyuan Su,
  • Jihao Zhang,
  • Hao Wang,
  • Yifeng Jiang,
  • Sharmistha Paul Dutta,
  • Mengxu Li,
  • Hazem Yousef,
  • Peter Zalden,
  • Kai Zhang,
  • Ruixue Zhu,
  • Xuan Liu,
  • Yingqi Wang,
  • Sophie E. Canton,
  • Diana Bregenholt Jakobsen,
  • Doriana Vinci,
  • Wenkai Zhang,
  • Jinggang Lan,
  • Tsu-Chien Weng,
  • Wenge Yang,
  • Michael Wulff,
  • Christopher Milne,
  • Dmitry Khakhulin,
  • Qingyu Kong

摘要

Roaming-mediated isomerization is a universal reaction mechanism in photochemistry, yet solvent-dependent pathways of roaming intermediates remain poorly understood, particularly for environmentally relevant halogen compounds involved in ozone depletion. Here, using femtosecond time-resolved X-ray solution scattering, we resolve the solvent-dependent roaming dynamics of CHBr3 in methanol and methylcyclohexane. By combining multi-method experimental analysis, machine learning-assisted ab initio molecular dynamics simulations, and density functional theory calculations, we uncover distinct solvent-steered reaction pathways. In methanol, roaming enhances solute-solvent interactions, leading to solvolysis before a stable isomer forms. In methylcyclohexane, roaming facilitates isomerization to a long-lived iso-CHBr2-Br product. Direct dissociation into CHBr2 + Br competes with both pathways in either solvent. By tracking bond-length oscillations and angular dynamics in real time, we visualize how the condensed-phase environment governs the branching ratio between competing pathways. Our findings establish solute-solvent interactions as key factors controlling roaming-mediated reactions in CHBr3, with broad implications for photochemical outcomes in solution.