Vibrational strong coupling (VSC) has emerged as a means for modifying chemical reactivity. Despite the intriguing discoveries and progresses in the field, the precise mechanisms that govern polaritonic chemistry still deserve further interrogation. Herein, we use the hydrolysis of ammonia borane in D₂O as an exemplary reaction and systematically investigate the influence of VSC on its reactivity. Experimental evidence of the coexistence of a resonant effect and reaction acceleration is observed in this system. In particular, we find that when the O–D stretching mode of D₂O is strongly coupled to a cavity mode, reaction acceleration is observed. The reaction rate acceleration factor, μ, is consistently observed to be dependent on the coupling conditions between the vibrational and cavity modes, and reaches a minimum at zero mode detuning, suggesting that a resonant effect is likely in play. In addition, we find that μ decreases with an increasing Rabi splitting. Based on these experimental findings, we propose that the overall influence of VSC on this reaction is likely determined collectively by the polaritonic bright and dark states. These findings could help shed new light on the intricate effects of VSC on ground-state reaction landscapes.

中文翻译：

---

极化子明态和暗态共同影响水解反应的反应性


振动强耦合 （VSC） 已成为一种改变化学反应性的手段。尽管该领域有有趣的发现和进展，但支配极化化学的确切机制仍然值得进一步研究。在此，我们以氨硼烷在 D₂O 中的水解作为示例反应，并系统地研究了 VSC 对其反应性的影响。在该系统中观察到共振效应和反应加速共存的实验证据。特别是，我们发现当 D₂O 的 O-D 拉伸模式与腔模式强耦合时，观察到反应加速。μ，一直观察到反应速率加速因子取决于振动模式和腔体模式之间的耦合条件，并在零模式失谐时达到最小值，这表明可能存在共振效应。此外，我们发现μ随着 Rabi 分裂的增加而降低。基于这些实验结果，我们提出 VSC 对该反应的总体影响可能由极化子亮态和暗态共同决定。这些发现可能有助于揭示 VSC 对基态反应景观的复杂影响。