The Marcus theory of electron transfer views fluctuating orientations of permanent dipoles as the nuclear mode bringing the donor and acceptor into the tunneling resonance. Electronic polarization of the solvent is excluded as the fast mode adiabatically following the electronic density. This view, valid for solids, does not apply to molecular liquids where molecular translations (density fluctuations) modulate the induction interaction of the donor-acceptor complex with the solvent. This mechanism of promoting radiationless electronic transitions is considered here in the framework of the perturbation liquid-state theory. The reorganization energy of electron transfer in nonpolar solvents is nonzero and reaches the values of 0.1-0.3 eV for typical molecular sizes and solvents used in applications. The reorganization energy scales quadratically with the molecular polarizability of the solvent and decays as the inverse fifth power with the size of the donor and acceptor. The combination of the entropic character of the density fluctuations, driven by re-packing of molecular cores, with the short range of induction solute-solvent interactions leads to the violation of the fluctuation-dissipation theorem for the variance of the donor-acceptor energy gap. An explicit, approximately hyperbolic, dependence of the reorganization energy on temperature is predicted. It leads to a non-Arrhenius kinetic law for the rate constant of electron transfer in nonpolar liquid solvents.

中文翻译：

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非极性介质中的电子转移。

马库斯的电子转移理论认为，永久性偶极子的波动方向是核模式，将供体和受体带入隧道共振。溶剂的电子极化被排除，因为绝热跟随电子密度的快速模式。该观点对固体有效，不适用于分子液体（分子涨落）调节供体-受体配合物与溶剂的诱导相互作用的分子液体。此处在摄动液态理论的框架内考虑了这种促进无辐射电子跃迁的机制。非极性溶剂中电子转移的重组能为非零值，对于典型的分子大小和应用中使用的溶剂，其重组能达到0.1-0.3 eV的值。重组能与溶剂的分子极化度呈二次方关系，并随着供体和受体的大小而变为倒数第五次幂。由分子核的重新堆积驱动的密度涨落的熵特性与感应溶质-溶剂相互作用的短范围相结合，导致违反了供体-受体能隙方差的涨落耗散定理。 。预测了重组能量对温度的明确的，近似双曲线的依赖性。对于非极性液体溶剂中的电子转移速率常数，这导致了非阿伦尼乌斯动力学定律。由分子核的重新堆积驱动的密度涨落的熵特性与感应溶质-溶剂相互作用的短范围相结合，导致违反了供体-受体能隙方差的涨落耗散定理。预测了重组能量对温度的明确的，近似双曲线的依赖性。对于非极性液体溶剂中的电子转移速率常数，这导致了非阿伦尼乌斯动力学定律。由分子核的重新堆积驱动的密度涨落的熵特性与感应溶质-溶剂相互作用的短范围相结合，导致违反了供体-受体能隙方差的涨落耗散定理。 。预测了重组能量对温度的明确的，近似双曲线的依赖性。对于非极性液体溶剂中的电子转移速率常数，这导致了非阿伦尼乌斯动力学定律。