Dagdigian Paul J, Alexander Millard H, Kłos Jacek
Department of Chemistry, The Johns Hopkins University, Baltimore, Maryland 21218-2685, USA.
Department of Chemistry and Biochemistry, University of Maryland, College Park, Maryland 20742-2021, USA.
J Chem Phys. 2015 Aug 7;143(5):054306. doi: 10.1063/1.4927704.
We present the quantum close-coupling treatment of spin-orbit induced transitions between the (1)D and (3)P states of an atom in collisions with a closed-shell spherical partner. In the particular case of O colliding with Xe, we used electronic structure calculations to compute the relevant potential energy curves and spin-orbit coupling matrix elements. We then carried out quantum scattering calculations of integral and differential quenching cross sections as functions of the collision energy. The calculated differential cross sections for electronic quenching are in reasonable agreement with measurements [Garofalo et al., J. Chem. Phys. 143, 054307 (2015)]. The differential cross sections exhibit pronounced oscillations as a function of the scattering angle. By a semiclassical analysis, we show that these oscillations result from quantum mechanical interference between two classical paths.
我们展示了与闭壳层球形伙伴碰撞的原子中，自旋轨道诱导的（1）D和（3）P态之间跃迁的量子密耦处理。在氧气与氙碰撞的特定情况下，我们使用电子结构计算来计算相关的势能曲线和自旋轨道耦合矩阵元。然后，我们进行了积分和微分猝灭截面作为碰撞能量函数的量子散射计算。计算得到的电子猝灭微分截面与测量结果[Garofalo等人，《化学物理杂志》143, 054307 (2015)]合理吻合。微分截面作为散射角的函数呈现出明显的振荡。通过半经典分析，我们表明这些振荡是由两条经典路径之间的量子力学干涉引起的。
