Photo-oxidation of Water by Molecular Oxygen: Isotope Exchange and Isotope Effects

被引：13

作者：

Buchachenko, Anatoly L. ^{[1
]}

Dubinina, Elena O. ^{[2
]}

机构：

[1] Russian Acad Sci, NN Semenov Chem Phys Inst, Moscow 119991, Russia

[2] Russian Acad Sci, Inst Geol & Geochem, Moscow 109017, Russia

来源：

JOURNAL OF PHYSICAL CHEMISTRY A | 2011年 / 115卷 / 15期

关键词：

CHARGE-TRANSFER COMPLEX; PARAMAGNETIC-COMPLEXES; ELECTRONIC-STRUCTURE; ORGANIC-LIGANDS; PHOTONUCLEATION; RADICALS; IDENTIFICATION; ABSORPTION; SIMULATION; VAPOR;

D O I：

10.1021/jp111613s

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

Photolysis of (17,18)O-labeled water in the presence of molecular oxygen is accompanied by transfer Of (17)O and (18)O isotopes from water to oxygen, demonstrating. that photoinduced oxidation of water does occur. The reaction exhibits the following isotope effect : oxidation of H(2)(17)Ois faster by 26% (in the Earth's magnetic field) and by 6.0% (in the field 0.5 T) than that of H(2)(18)O. The effect is supposed to arise in the two spin-selective, isotope-sorting reactions recombination and disproportionation-in the pairs of encountering HO(2) radicals. The former is spin allowed from the singlet state; the latter occurs only in the triplet one. Nuclear spin sorting produced by these reactions proceeds in opposite directions with the dominating contribution of recombination, which provides observable (17)O/(18)O isotope fractionation in favor of magnetic isotope (17)O. Neither isotope exchange nor the reaction itself Occurs in the dark.

引用

页码：3196 / 3200

页数：5

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