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首页> 外文期刊>Journal of photochemistry and photobiology, C. Photochemistry reviews >Spin-orbit coupling induced electron spin polarization in photoinduced electron transfer reactions
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Spin-orbit coupling induced electron spin polarization in photoinduced electron transfer reactions

机译：自旋轨道耦合在光诱导电子转移反应中诱导电子自旋极化

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摘要

The observation of net-absorptive chemically induced dynamic electron polarization (CIDEP) spectra induced by spin-orbit coupling (SOC) interactions due to heavy atoms gives proof of the generation of a contact radical pair (RP) or triplet exciplex as the intermediate. Recent time-resolved EPR and pulsed EPR studies on the spin dynamics are reviewed. The SOC interaction causes simultaneous changes in the orbital and spin operators, leading to sublevel-selective back electron transfer from the short-lived intermediate to the singlet ground state. The intrinsic enhancement factor of the SOC-induced polarization increases with increasing atomic number of the heavy atom substituent. On the other hand, the radical yield decreases remarkably with increasingly heavy atoms. The build-up rate of the SOC-induced CIDEP signal gives the formation rate of the RP-type triplet exciplex. Quantitative analyses of the spin dynamics provide kinetic parameters such as the back electron transfer rate, escape rate, relaxation times of the precursor of the excited triplet state and free radicals. It has been shown that the experiments on the magnetic field effect on the radical yield complement the spin polarization dynamics studies.
机译：由重原子引起的自旋-轨道耦合（SOC）相互作用引起的净吸收化学诱导动态电子极化（CIDEP）光谱的观察提供了作为中间产物的接触自由基对（RP）或三重态激基复合物的产生的证据。审查了最近的时间分辨EPR和脉冲EPR研究自旋动力学。 SOC相互作用会同时导致轨道和自旋算子发生变化，从而导致子级选择性背电子从短寿命中间体转变为单重态基态。 SOC诱导的极化的本征增强因子随重原子取代基的原子数增加而增加。另一方面，随着重原子的增加，自由基产率显着降低。 SOC诱导的CIDEP信号的累积速率给出了RP型三重态激基复合物的形成速率。自旋动力学的定量分析提供了动力学参数，例如背电子传输速率，逸出速率，激发三重态的前体和自由基的弛豫时间。已经表明，磁场对自由基产率的影响的实验补充了自旋极化动力学研究。

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