Gladkikh V S, Angulo G, Burshtein A I
Weizmann Institute of Science, Rehovot 76100, Israel.
J Phys Chem A. 2007 May 10;111(18):3458-64. doi: 10.1021/jp068375f. Epub 2007 Apr 18.
The quantum yields of triplets and free radicals (or radical ions) that escaped recombination in photochemically created primary radical pairs (or radical ion pairs) are calculated. As the products of monomolecular photodissociation, the neutral radicals appear at contact, while the ions are initially distributed over the space due to distant photoionization (bimolecular electron transfer) in the liquid solution. The diffusional dependence of the quantum yields is shown to be different when recombination starts from contact or from separated reactants. The experimental data for recombination of ionized perylene with aromatic amine counterions is well fitted with the noncontact initial distribution provided the recombination is also noncontact and even more distant than ionization.
计算了在光化学产生的初级自由基对（或自由基离子对）中逃脱复合的三重态和自由基（或自由基离子）的量子产率。作为单分子光解离的产物，中性自由基在接触时出现，而离子由于液体溶液中的远程光电离（双分子电子转移）最初分布在空间中。当复合从接触或分离的反应物开始时，量子产率的扩散依赖性显示出不同。如果复合也是非接触的且比电离更远，则离子化苝与芳族胺抗衡离子复合的实验数据与非接触初始分布拟合良好。
