Electron transfer in confined electromagnetic fields.
Electron transfer in confined electromagnetic fields.
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DOI：
10.1063/1.5095940
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发表时间：
2019-02
期刊：
影响因子：
--
通讯作者：
A. Semenov;A. Nitzan
中科院分区：
文献类型：
--
作者：
A. Semenov;A. Nitzan
由于纳米光子学的快速发展，分子（原子）电子与反射腔真空场之间的相互作用引起了人们极大的兴趣。这种相互作用属于空腔量子电动力学领域，可以实质性地影响分子系统的输运性质。在这项工作中，我们考虑了在空穴模式存在下的非绝热电子转移过程。我们提出了带电分子系统与量子化腔电磁场相互作用的广义框架，并将其应用于受限真空电磁场中供体和受体之间的电子转移问题。有效系统哈密顿量对应于包含自偶极子能量项的统一拉比和自旋玻色子模型。考虑了两种极限情况：一种是假设电子比空腔模式快得多，另一种是电子隧穿时间明显大于模式周期。在这两种情况下，通过耦合Marcus倒转区域的腔模式可以产生显著的速率增强。这项工作的结果为利用可见和红外等离子体控制电子转移过程提供了新的可能性。
The interaction between molecular (atomic) electron(s) and the vacuum field of a reflective cavity generates significant interest, thanks to the rapid developments in nanophotonics. Such interaction which lies within the realm of cavity quantum electrodynamic can substantially affect the transport properties of molecular systems. In this work, we consider a nonadiabatic electron transfer process in the presence of a cavity mode. We present a generalized framework for the interaction between a charged molecular system and a quantized electromagnetic field of a cavity and apply it to the problem of electron transfer between a donor and an acceptor placed in a confined vacuum electromagnetic field. The effective system Hamiltonian corresponds to a unified Rabi and spin-boson model which includes a self-dipole energy term. Two limiting cases are considered: one where the electron is assumed much faster than the cavity mode and another in which the electron tunneling time is significantly larger than the mode period. In both cases, a significant rate enhancement can be produced by coupling to the cavity mode in the Marcus inverted region. The results of this work offer new possibilities for controlling electron transfer processes using visible and infrared plasmonics.