UV photolysis of I3- in solution -: Multiple product channels detected by transient hyperspectral probing
UV photolysis of I3- in solution -: Multiple product channels detected by transient hyperspectral probing
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DOI：
10.1016/j.cplett.2008.07.001
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发表时间：
2008-08-20
影响因子：
2.8
通讯作者：
Ruhman, Sanford
中科院分区：
文献类型：
--
作者：
Baratz, Adva;Ruhman, Sanford
利用飞秒高光谱探测，在几种极性液体中跟踪三碘化合物的复合。结果显示，产物的吸光度在几十皮秒内变窄和蓝移，与双链重组的延迟阶段相吻合。全局动力学分析表明，两者都可以被指定为不同的碎片群，而不是游离的溶剂化二碘化合物，最有可能是笼状的[中心点I-2(-)；中心点I-2(-)]接触对。碎片之间的相互作用被认为改变了二碘化物吸收带的振子强度和跃迁能，光谱演化反映了接触对的重组以再生I-3(-)。笼状碎片之间的电荷转移被认为是决定复合速率的步骤，解释了它的延迟性质。(C)2008爱思唯尔B.V.保留所有权利。
Recombination of triiodide is followed in several polar liquids using femtosecond hyperspectral probing. Results reveal narrowing and blue shifting in product absorbance for tens of picoseconds coinciding with a delayed stage of geminate recombination. Global kinetic analysis suggests both can be assigned to a distinct fragment population other than free solvated diiodide, most likely caged [center dot I-2(-);center dot I-2(-)] contact pairs. Interaction between the fragments is proposed to alter oscillator strengths and transition energies of the diiodide absorption bands, with the spectral evolution reflecting recombination of contact pairs to regenerate I-3(-). Charge transfer between the caged fragments is proposed to be the step determining the rates of recombination explaining its delayed nature. (C) 2008 Elsevier B.V. All rights reserved.