Theory for polariton-assisted remote energy transfer.
Theory for polariton-assisted remote energy transfer.
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DOI：
10.1039/c8sc00171e
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发表时间：
2018-08-28
期刊：
影响因子：
8.4
通讯作者：
Yuen-Zhou J
中科院分区：
文献类型：
--
作者：
Du M;Martínez-Martínez LA;Ribeiro RF;Hu Z;Menon VM;Yuen-Zhou J
提出了一种综合理论，从机械上阐明与电磁场强耦合的分子之间的长程能量转移。光与物质之间的强耦合产生混合态（极化子），其离域和电磁特性允许对分子系统的光谱和化学反应性进行新的修改。最近的实验表明，与光学微腔模式强耦合的分子之间存在显着的与距离无关的长程能量转移。为了阐明这种现象的机制，我们提出了第一个基于供体和/或受体生色团与表面等离子体激元强耦合的极化子辅助远程能量转移（PARET）的综合理论。我们的理论的应用表明 PARET 达到微米级确实是可能的。特别是，我们报告了 PARET 的两种机制：在一种情况下，与单一类型生色团的强耦合导致主要由表面等离子体介导的转移，而在另一种情况下，与两种类型生色团的强耦合产生由振动弛豫介导的能量转移途径。重要的是，我们强调了一致性增强或恶化这些过程的条件。例如，虽然与捐赠者的排他性强耦合可以增强向接受者的转移，但事实证明相反的情况并非如此。然而，与受体的强耦合可以改变能级，从受体转移到供体，从而产生发色团角色逆转或“狂欢效应”。这项理论研究证明了受限电磁场控制和介导 PARET 的潜力，从而为分子系统之间远程介尺度相互作用的设计打开了大门。
A comprehensive theory is presented to mechanistically elucidate the long-range energy transfer between molecules strongly coupled to electromagnetic fields. Strong-coupling between light and matter produces hybridized states (polaritons) whose delocalization and electromagnetic character allow for novel modifications in spectroscopy and chemical reactivity of molecular systems. Recent experiments have demonstrated remarkable distance-independent long-range energy transfer between molecules strongly coupled to optical microcavity modes. To shed light on the mechanism of this phenomenon, we present the first comprehensive theory of polariton-assisted remote energy transfer (PARET) based on strong-coupling of donor and/or acceptor chromophores to surface plasmons. Application of our theory demonstrates that PARET up to a micron is indeed possible. In particular, we report two regimes for PARET: in one case, strong-coupling to a single type of chromophore leads to transfer mediated largely by surface plasmons while in the other case, strong-coupling to both types of chromophores creates energy transfer pathways mediated by vibrational relaxation. Importantly, we highlight conditions under which coherence enhances or deteriorates these processes. For instance, while exclusive strong-coupling to donors can enhance transfer to acceptors, the reverse turns out not to be true. However, strong-coupling to acceptors can shift energy levels in a way that transfer from acceptors to donors can occur, thus yielding a chromophore role-reversal or “carnival effect”. This theoretical study demonstrates the potential for confined electromagnetic fields to control and mediate PARET, thus opening doors to the design of remote mesoscale interactions between molecular systems.
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