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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Spin exchange of nitroxyl radicals in H 2_O and D 2_O
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Spin exchange of nitroxyl radicals in H 2_O and D 2_O

机译：H 2_O和D 2_O中硝氧基自由基的自旋交换

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摘要

By means of continuous wave electron spin resonance (cw ESR) in the X and L bands, the spin exchange of series of different concentrations of the spin probes 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO), 4-hydroxy-2,2,6,6- tetramethylpiperidine-1-oxyl (TEMPOL), and 4-(trimethylamino)-2,2,6,6- tetramethylpiperidine-1-oxyl iodide (CAT-1) in H _2O and D _2O have been examined. The rate constants k _e of the spin exchange have been determined by complete spectra simulations, as well as directly from hyperfine line broadenings and concentration depending line shifts. The obtained results showed a good agreement. Their respective differences {k _e(H _2O) - k _e(D_ 2O)} could be determined for the first time. They reflect the different influence of the solvents on the spin dynamics but confirm the decrease of the reaction rate in D _2O, caused by the higher degree of order in this liquid. The spectroscopic and kinetic results presented in this paper establish a further kind of isotopic effect.
机译：通过X和L波段的连续波电子自旋共振（cw ESR），自旋交换一系列不同浓度的自旋探针2,2,6,6-四甲基哌啶-1-氧基（TEMPO），4- H _2O和D中的羟基-2,2,6,6-四甲基哌啶-1-氧基（TEMPOL）和4-（三甲基氨基）-2,2,6,6-四甲基哌啶-1-氧基碘（CAT-1）已检查_2O。自旋交换的速率常数k _e已通过完整的光谱模拟以及直接根据超细线加宽和浓度（取决于线位移）确定。获得的结果显示出良好的一致性。可以第一次确定它们各自的差异{k _e（H _2O）-k _e（D_2O）}。它们反映了溶剂对自旋动力学的不同影响，但证实了D _2O中反应速率的降低，这是由于该液体中较高的有序度引起的。本文提出的光谱和动力学结果建立了另一种同位素效应。

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