Wu Yanze, Miao Gaohan, Subotnik Joseph E
Department of Chemistry, University of Pennsylvania, Philadelphia, Pennsylvania 19104, United States.
J Phys Chem A. 2020 Sep 17;124(37):7355-7372. doi: 10.1021/acs.jpca.0c04562. Epub 2020 Sep 1.
Within the context of a simple avoided crossing, we investigate the effect of a complex-valued diabatic coupling in determining spin-dependent rate constants and scattering states. We find that, if the molecular geometry is not linear and the Berry force is not zero, one can find significant spin polarization of the products. This study emphasizes that, when analyzing nonadiabatic reactions with spin orbit coupling (and a complex-valued Hamiltonian), one must consider how Berry force affects nuclear motion-at least in the context of gas phase reactions. Work is currently ongoing as far as extrapolating these conclusions to the condensed phase, where interesting spin selection has been observed in recent years.
在简单的避免交叉的背景下，我们研究了复数值绝热耦合在确定自旋相关速率常数和散射态方面的作用。我们发现，如果分子几何结构不是线性的且贝里力不为零，那么产物中会出现显著的自旋极化。该研究强调，在分析具有自旋轨道耦合（以及复数值哈密顿量）的非绝热反应时，至少在气相反应的背景下，必须考虑贝里力如何影响核运动。目前正在进行将这些结论外推到凝聚相的工作，近年来在凝聚相中已观察到有趣的自旋选择现象。
