Salam A
Department of Chemistry, Wake Forest University, Winston-Salem, North Carolina 27109, United States.
J Phys Chem A. 2021 May 6;125(17):3549-3555. doi: 10.1021/acs.jpca.0c11053. Epub 2021 Feb 17.
Relay of resonant excitation energy between two chiral molecules by an inert third particle is studied using molecular quantum electrodynamics theory. A single virtual photon propagates between each interacting pair. Fourth-order diagrammatic time-dependent perturbation theory is employed to compute the matrix element. Rate terms dependent upon the chirality of the donor and acceptor species are extracted using the Fermi golden rule. Interestingly, the mediated rate is discriminatory. For freely tumbling particles it exhibits an inverse-square dependence on each interparticle separation distance, indicating a purely radiative exchange mechanism. Furthermore, the isotropic rate is found to be a maximum for a collinear geometry and vanishes when the angle between the donor, mediator, and acceptor is 90°. The indirect rate is compared with direct transfer between two chiral molecules. Insight is gained into discriminatory migration of energy in a dielectric medium.
利用分子量子电动力学理论研究了惰性第三粒子在两个手性分子之间的共振激发能量传递。单个虚光子在每对相互作用的粒子之间传播。采用四阶图解含时微扰理论来计算矩阵元。利用费米黄金规则提取依赖于供体和受体物种手性的速率项。有趣的是，介导速率具有选择性。对于自由翻滚的粒子，它对每个粒子间分离距离呈现反平方依赖关系，表明是一种纯辐射交换机制。此外，发现各向同性速率在共线几何结构中最大，当供体、介质和受体之间的角度为90°时消失。将间接速率与两个手性分子之间的直接转移进行了比较。深入了解了电介质中能量的选择性迁移。
