Effects of weak magnetic fields on free radical recombination reactions

被引:318
|
作者
Timmel, CR
Till, U
Brocklehurst, B
McLauchlan, KA
Hore, PJ
机构
[1] Univ Oxford, Phys & Theoret Chem Lab, Oxford OX1 3QZ, England
[2] Univ Sheffield, Dept Chem, Sheffield S3 7HF, S Yorkshire, England
基金
英国工程与自然科学研究理事会;
关键词
D O I
10.1080/00268979809483134
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
The radical pair mechanism is used to elucidate bow applied magnetic fields that are weaker in strength than typical hyperfine interactions can influence the yields and kinetics of recombination reactions of free radicals in solution. The so-called low field effect is shown to arise from coherent superpositions of degenerate electron-nuclear spin states in a spin-correlated radical pair in zero field. A weak applied magnetic field causes these (zero-quantum) coherences to oscillate, leading to coherent interconversion of singlet and triplet electronic states of the radical pair and hence changes in the yields of recombination products and of the free radicals that escape into solution. For singlet geminate radical pairs, the low field effect leads to a boost in the concentration of free radicals, which may be relevant in the context of in vivo biological effects of electromagnetic fields. Using analytical approaches in limiting cases, the maximum possible low field effects are calculated fbr a variety of radical pairs. Sizeable changes in reaction yields (similar to 20%) are found for almost any radical pair provided the spin-correlation persists long enough for significant evolution of the electron spins under the influence of the weak applied field. The conditions necessary for observing effects as large as similar to 20% are discussed.
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页码:71 / 89
页数:19
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