On the Role of Symmetry in Vibrational Strong Coupling: The Case of Charge-Transfer Complexation
On the Role of Symmetry in Vibrational Strong Coupling: The Case of Charge-Transfer Complexation
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DOI：
10.1002/anie.202002527
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发表时间：
2020-04-16
影响因子：
16.6
通讯作者：
Ebbesen, Thomas W.
中科院分区：
文献类型：
--
作者：
Pang, Yantao;Thomas, Anoop;Ebbesen, Thomas W.
众所周知，对称性在化学反应中起着关键作用。在这里，我们探讨了它的作用，在振动强耦合（VSC）的电荷转移（CT）络合反应。通过研究三甲基苯-I-2CT络合物，我们发现VSC引起CT络合物的平衡常数K-DA的大的变化，反映了反应的Δ G度值的修改。此外，通过将微流体腔模式调谐到三甲基化苯的不同IR振动，Δ G度仅取决于耦合的正常模式的对称性而增加或减少。这一结果揭示了对称性在VSC中的关键作用，并反过来解释了为什么VSC引起的化学变化的幅度远远大于拉比分裂，即VSC引起的能量扰动。这些发现进一步证实了VSC是分子科学的强大而通用的工具。
It is well known that symmetry plays a key role in chemical reactivity. Here we explore its role in vibrational strong coupling (VSC) for a charge-transfer (CT) complexation reaction. By studying the trimethylated-benzene-I-2 CT complex, we find that VSC induces large changes in the equilibrium constant K-DA of the CT complex, reflecting modifications in the Delta G degrees value of the reaction. Furthermore, by tuning the microfluidic cavity modes to the different IR vibrations of the trimethylated benzene, Delta G degrees either increases or decreases depending only on the symmetry of the normal mode that is coupled. This result reveals the critical role of symmetry in VSC and, in turn, provides an explanation for why the magnitude of chemical changes induced by VSC are much greater than the Rabi splitting, that is, the energy perturbation caused by VSC. These findings further confirm that VSC is powerful and versatile tool for the molecular sciences.