Polariton-Mediated Electron Transfer via Cavity Quantum Electrodynamics
Polariton-Mediated Electron Transfer via Cavity Quantum Electrodynamics
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DOI：
10.1021/acs.jpcb.0c03227
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发表时间：
2020-07-23
影响因子：
3.3
通讯作者：
Huo, Pengfei
中科院分区：
文献类型：
--
作者：
Mandal, Arkajit;Krauss, Todd D.;Huo, Pengfei
利用解析速率常数理论和直接量子动力学模拟研究了模型系统中极化介导的电子转移反应。我们证明了通过将分子系统与光学腔内的量子化辐射场耦合，可以显著增强或抑制明亮的给体态和黑暗的受体态之间的光诱导电荷转移反应。这是因为量子光-物质相互作用可以影响施主态（即混合光-物质激发）与分子受体态之间的有效驱动力和电子耦合。在光子和电子激发的共振条件下，可以通过改变光-物质耦合强度来调节有效驱动力；在非共振条件下，通过改变分子腔失谐可以达到相同的效果。我们进一步证明，使用电子耦合和光物质耦合有助于扩展整个系统的有效耦合，即使对于携带零跃迁偶极子的暗态也是如此。从理论上讲，我们发现量子电动力学哈密顿量中的反旋转项和偶极子自能对于获得精确的极化子本征谱和极化子中介的电荷转移速率常数非常重要，特别是在超强耦合区。
We investigate the polariton-mediated electron transfer reaction in a model system with analytic rate constant theory and direct 6 quantum dynamical simulations. We demonstrate that the photoinduced charge transfer reaction between a bright donor state and dark acceptor state can be significantly enhanced or suppressed by coupling the molecular system to the quantized radiation field inside an optical cavity. This is because the quantum light-matter interaction can influence the effective driving force and electronic couplings between the donor state, which is the hybrid light-matter excitation, and the molecular acceptor state. Under the resonance condition between the photonic and electronic excitations, the effective driving force can be tuned by changing the light-matter coupling strength; for an off-resonant condition, the same effect can be accomplished by changing the molecule-cavity detuning. We further demonstrate that using both the electronic coupling and light-matter coupling helps to extend the effective couplings across the entire system, even for the dark state that carries a zero transition dipole. Theoretically, we find that both the counter-rotating terms and the dipole self-energy in the quantum electrodynamics Hamiltonian are important for obtaining an accurate polariton eigenspectrum as well as the polariton-mediated charge transfer rate constant, especially in the ultrastrong coupling regime.