Department of Physics, Volgograd State University, University Avenue, 100, Volgograd, 400062, Russia.
J Phys Chem A. 2009 Dec 3;113(48):13528-40. doi: 10.1021/jp901863t.
The photoionization of perylene by tetracyanoethylene (TCNE) in liquid solutions is reconsidered within the corrected energy scheme for a double channel electron transfer: to the ground and excited states of the produced ion pair. The complex space dependence of a total (double channel) rate of multiphonon transfer is specified and compared to the recently proposed monoexponential model. The fitting of the forward electron transfer (ionization) is essentially improved, and the real electron coupling and tunneling parameters are firmly established. The same has been done for the geminate recombination/separation kinetics, accounting theoretically for the hot recombination experienced by 2/3 of the initially produced ion pairs. Only 1/3 of them is left for subsequent thermal recombination and even less are left for their separation into free ions. The yields of the latter, strongly dependent on the initial concentration of TCNE, are brought into reasonable coincidence with the theoretical predictions by a renormalization of the empirically calibrated ion densities especially at large concentrations. Altogether, this is a precedent spin-less treatment of photoionization well-fitted to the experimental data at all times (from the excitation until charge separation), with a single set of varying parameters.
在修正的双电子转移通道（到生成的离子对的基态和激发态）的能量方案内，重新考虑了在液体溶液中由四氰乙烯（TCNE）引起的苝的光电离。指定了总（双通道）多声子转移的复杂空间依赖性，并与最近提出的单指数模型进行了比较。向前电子转移（电离）的拟合得到了显著改善，并且确定了实际电子耦合和隧道参数。对于成对复合/分离动力学也是如此，从理论上解释了 2/3 的初始生成的离子对所经历的热复合。只有其中的 1/3 可用于随后的热复合，甚至更少的部分可用于它们分离成自由离子。这些自由离子的产率强烈依赖于 TCNE 的初始浓度，通过对经验校准的离子密度进行归一化处理（特别是在高浓度下），与理论预测达到了很好的一致性。总的来说，这是一个无自旋的光电离的先例处理，始终与实验数据（从激发到电荷分离）很好地吻合，并且只有一组变化的参数。
