Voevodsky Institute of Chemical Kinetics and Combustion, 630090 Novosibirsk, Russia and Novosibirsk State University, 630090 Novosibirsk, Russia.
J Chem Phys. 2019 Nov 14;151(18):184112. doi: 10.1063/1.5127217.
Basic algebraic arguments demonstrate that the probability of radical pair recombination in low field for an arbitrary pair with Hamiltonian confined to Zeeman and isotropic hyperfine interactions contains two additive contributions linear with applied field with equal, but opposite in sign, proportionality factors. Their weights are determined by the probability of having all nuclear spins along the field in the initial electron-singlet state of the pair, and in the case of equilibrium with respect to nuclear spins, the two contributions completely compensate the field dependences of each other, producing an additive term in the singlet yield with zero derivative. However, if the nuclear set is polarized, a linear skew proportional to polarization appears, introducing anisotropy in the intrinsically spherically symmetric system. The key element in this derivation is guaranteed nondegeneracy of the eigenvalues of the "penultimate" (M - 1) block of the Hamiltonian for a radical with any number of distinct spin-1/2 nuclei in zero field, which leads to guaranteed applicability of the first-order nondegenerate perturbation theory with nonvanishing linear in field admixture of states, persisting all the way into the final expression for singlet yield for a pair with an arbitrary isotropic hyperfine structure. We argue that this behavior of the field dependence of recombination yield is representative of a radical pair of an arbitrarily complex hyperfine structure; this may be a possible mechanism for anisotropic response ("chemical compass") for an isotropic radical pair based system with isotropic-only internal interactions and anisotropy introduced via the initial state of nuclei, while such an approach may complement the usually needed numerical simulations.
基本代数学论证表明,对于任意一对具有受限至塞曼和各向同性超精细相互作用的哈密顿量的自由基对,在低场中的自由基对复合的概率包含两个与外加场线性相加的贡献,其比例因子相等,但符号相反。它们的权重由自由基对的电子单态初始状态下所有核自旋沿场的概率以及相对于核自旋处于平衡的情况下确定,如果核自旋被极化,则会出现与极化成正比的线性偏斜,从而在本质上各向同性的系统中引入各向异性。这种推导的关键要素是保证自由基在零场中具有任意数量的分立自旋-1/2核的“倒数第二”(M-1)块哈密顿量的本征值非简并,这保证了一阶非简并微扰理论的适用性,其中存在非零的与场线性混合的态,一直持续到任意各向同性超精细结构对自由基对的单态产率的最终表达式。我们认为,这种复合产率的场依赖性的行为代表了任意复杂超精细结构的自由基对;这可能是基于各向同性自由基对的各向异性响应(“化学罗盘”)的一种可能机制,该自由基对具有各向同性的内部相互作用,并且通过核的初始状态引入各向异性,而这种方法可能会补充通常需要的数值模拟。