International Tomography Center SB RAS, 630090 Novosibirsk, Russia.
Voevodsky Institute of Chemical Kinetics and Combustion SB RAS, 630090 Novosibirsk, Russia.
Int J Mol Sci. 2023 Apr 20;24(8):7555. doi: 10.3390/ijms24087555.
The influence of magnetic fields on chemical reactions, including biological ones, has been and still is a topical subject in the field of scientific research. Experimentally discovered and theoretically substantiated magnetic and spin effects in chemical radical reactions form the basis of research in the field of spin chemistry. In the present work, the effect of a magnetic field on the rate constant of the bimolecular spin-selective recombination of radicals in the bulk of a solution is considered theoretically for the first time, taking into account the hyperfine interaction of radical spins with their magnetic nuclei. In addition, the paramagnetic relaxation of unpaired spins of the radicals and the non-equality of their g-factors that also influence the recombination process are taken into account. It is found that the reaction rate constant can vary in magnetic field from a few to half a dozen percent, depending on the relative diffusion coefficient of radicals, which is determined by the solution viscosity. It is shown that the consideration of hyperfine interactions gives rise to the presence of resonances in the dependence of the rate constant on the magnetic field. The magnitudes of the magnetic fields of these resonances are determined by the hyperfine coupling constants and difference in the g-factors of the recombining radicals. Analytical expressions for the reaction rate constant of the bulk recombination for magnetic fields larger than hfi (hyperfine interaction) constants are obtained. In general, it is shown for the first time that accounting for hyperfine interactions of radical spins with magnetic nuclei significantly affects the dependence of the reaction rate constant of the bulk radical recombination on the magnetic field.
磁场对化学反应的影响,包括生物化学反应的影响,一直是科学研究领域的一个热门话题。在化学自由基反应中发现的实验磁性和自旋效应以及从理论上得到证实的这些效应,构成了自旋化学领域研究的基础。在目前的工作中,首次从理论上考虑了自由基在溶液体相中的双分子自旋选择性复合反应的速率常数受磁场的影响,其中考虑了自由基自旋与其磁核的超精细相互作用。此外,还考虑了自由基未成对自旋的顺磁弛豫以及也会影响复合过程的其 g 因子的不等性。结果发现,反应速率常数在磁场中可以变化几个百分点到半打百分点,这取决于决定溶液粘度的自由基的相对扩散系数。结果表明,超精细相互作用的考虑导致在速率常数对磁场的依赖关系中存在共振。这些共振的磁场大小由超精细耦合常数和复合自由基的 g 因子的差异决定。获得了磁场大于超精细相互作用(hfi)常数时的体相复合反应速率常数的解析表达式。总的来说,首次表明自由基自旋与磁核的超精细相互作用显著影响了自由基在体相复合反应速率常数对磁场的依赖关系。
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