发表机构
University of Copenhagen; Niels Bohr Institute, University of Copenhagen; Flatiron Institute; Bates College; City College of New York; The Graduate Center, City University of New York（哥本哈根大学; 尼尔斯·玻尔研究所，哥本哈根大学; 平顿研究所; 贝茨学院; 纽约市立学院; 纽约市立大学研究生院）
机构由 AI 辅助整理，请以论文原文为准。AI 中文总结
本研究采用扩展的HEOM张量网络方法，分析振动强耦合下极化子化学的竞争反应路径，揭示腔诱导的局部跃迁变化如何改变动力学瓶颈并重新分配反应通量，为理解路径特异性反应性提供机制框架。
AI 中文摘要
最近的实验表明，分子与腔模之间的强光-物质耦合可以显著改变化学反应速率和产率。尽管提出了多种机制，但对振动强耦合如何改变反应动力学的微观理解仍不完整。在此，我们通过考虑具有多个相关跃迁频率的反应坐标和一般谐波环境，采用一个通用的量子动力学框架来分析极化子化学中的竞争反应路径。我们扩展了层次运动方程（HEOM）方法的张量网络公式，以计算振动态之间的概率流，利用有效谱密度的简洁公式和将马尔可夫浴模式受控压缩为系统级跳变算符。这使我们能够分解所得的状态间概率流，揭示腔诱导的单个跃迁变化如何通过多步反应网络传播。我们发现，这些局部修改可以改变动力学瓶颈，并选择性地在竞争路径之间重新分配反应通量，在不可逆条件下改变分支比，而在可逆状态下基本不影响平衡产率。最后，对于耦合的反应坐标、旁观者模式和腔环境，我们发现由混合衰变通道之间的干涉产生的结构化、不对称速率曲线。总之，这些结果为理解振动强耦合下路径特异性化学反应性提供了一个机制框架。
英文摘要
Recent experiments suggest that strong light-matter coupling between molecules and cavity modes can significantly modify chemical reaction rates and yields. Despite multiple proposed mechanisms, a clear microscopic understanding of how vibrational strong coupling alters reaction kinetics remains incomplete. Here, we employ a general quantum-dynamical framework for analyzing competing reaction pathways in polaritonic chemistry by considering reaction coordinates with multiple relevant transition frequencies and general harmonic environments. We extend on a tensor-network formulation of the hierarchical equations of motion (HEOM) method to compute probability currents between vibrational states, leveraging a concise formulation for effective spectral densities and a controlled compression of Markovian bath modes into system-level jump operators. This allows us to decompose the resulting state-to-state probability currents, revealing how cavity-induced changes in individual transitions propagate through multistep reaction networks. We find that these local modifications can alter kinetic bottlenecks and selectively redistribute reaction flux between competing pathways, changing branching ratios under irreversible conditions without substantially affecting the equilibrium yield in the reversible regime. Finally, for coupled reaction-coordinate, spectator-mode, and cavity environments, we find structured, asymmetric rate profiles arising from interference between hybridized decay channels. Together, these results provide a mechanistic framework for understanding pathway-specific chemical reactivity under vibrational strong coupling.
Comments15 pages, 9 figures. Supplemental: 25 pages, 8 figures, 3 tables
