Controlling electron transfer in strong time-dependent fields: Theory beyond the Golden Rule approximation
Controlling electron transfer in strong time-dependent fields: Theory beyond the Golden Rule approximation
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控制强时间相关场中的电子转移：超越黄金法则近似的理论
DOI：
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发表时间：
2000
期刊：
影响因子：
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通讯作者：
P. Hänggi
中科院分区：
文献类型：
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作者：
L. Hartmann;I. Goychuk;P. Hänggi
在这项工作中，我们应用一个推广的Zusman模型来研究外加周期电场对电子转移(ET)反应动力学的影响。这种方法在隧道耦合中是非微扰的，超越了传统的黄金法则描述，同时包括绝热和非绝热电子转移机制。在高频驱动下，得到了ET率的显式表达式，并与精确的数值结果进行了比较。我们新的分析结果构成了一个有用的近似方案，只要动力学可以用单指数松弛来表征。我们进一步证明，在强而快的振荡场的存在下，黄金法则的描述会得到极大的改进。此外，我们还讨论了有趣的现象，如布居反转和驱动诱导从绝热反应动力学到非绝热反应动力学的转变。
In this work we apply a generalized Zusman model to study the influence of an external periodic electric field on the dynamics of electron transfer (ET) reactions coupled to an overdamped reaction coordinate which is treated semiclassically. Being nonperturbative in the tunneling coupling this approach goes beyond the conventional Golden Rule description and includes both adiabatic and nonadiabatic electron transfer regimes. Explicit expressions for the ET rates are derived in the high-frequency driving regime and compared with exact numerical results. Our novel analytical findings constitute a useful approximation scheme, as long as the dynamics can be characterized by a single exponential relaxation. We further demonstrate that the Golden Rule description becomes drastically improved in the presence of strong, fast oscillating fields. Moreover, we discuss interesting phenomena such as an inversion of populations and a driving induced transition from an adiabatic to a nonadiabatic reaction dynamics.