过氧化氢水溶液200 nm光解产生的羟基自由基的双生复合
Geminate recombination of hydroxyl radicals generated in 200 nm photodissociation of aqueous hydrogen peroxide
摘要：
通过266 nm处的瞬态吸收，观察了过氧化氢水溶液在200 nm光诱导解离过程中产生的羟基自由基的皮秒动力学。结果表明，这些动力学是近指数，衰减时间约为。30 ps。H_2O_2分解的瞬时量子产率为0.56，从溶剂笼逃逸到水本体的羟基自由基的分数为64- 68%。这些重组动力学表明，强大的笼双生羟基自由基的水。现象学上，这些动力学可以合理化的扩散的氢氧化物自由基的浅势阱（溶剂笼）的Onsager半径为0.24 nm。
英文摘要：
The picosecond dynamics of hydroxyl radicals generated in 200 nm photoinduced dissociation of aqueous hydrogen peroxide have been observed through their transient absorbance at 266 nm. It is shown that these kinetics are nearly exponential, with a decay time of ca. 30 ps. The prompt quantum yield for the decomposition of H2O2 is 0.56, and the fraction of hydroxyl radicals escaping from the solvent cage to the water bulk is 64-68%. These recombination kinetics suggest strong caging of the geminate hydroxyl radicals by water. Phenomenologically, these kinetics may be rationalized in terms of the diffusion of hydroxide radicals out of a shallow potential well (a solvent cage) with an Onsager radius of 0.24 nm.
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