Applied Physics, Division of Materials Science, Department of Engineering Science and Mathematics, Luleå University of Technology, 97187 Luleå, Sweden.
J Chem Phys. 2017 Sep 7;147(9):094308. doi: 10.1063/1.5000573.
A semiclassical method based on surface-hopping techniques is developed to model the dynamics of radiative association with electronic transitions. It can be proven that this method is an extension of the established semiclassical formula used in the characterization of diatomic molecule-formation. Our method is tested for diatomic molecules. It gives the same cross sections as the former semiclassical formula but, contrary to the former method, it allows us to follow the fate of the trajectories after the emission of a photon. This means that we can characterize the rovibrational states of the stabilized molecules. Using semiclassical quantization, we can obtain quantum state-resolved cross sections or emission spectra for the radiative association process. The calculated semiclassical state-resolved spectra show general agreement with the result of quantum mechanical perturbation theory. Furthermore, our surface-hopping model is not only applicable for the description of radiative association but it can be used for semiclassical characterization of any molecular process where spontaneous emission occurs.
一种基于表面跳跃技术的半经典方法被开发出来，用于模拟与电子跃迁相关的辐射缔合的动力学。可以证明，这种方法是在双原子分子形成的特征描述中使用的已有半经典公式的扩展。我们的方法针对双原子分子进行了测试。它给出了与前一个半经典公式相同的截面，但与前一种方法不同的是，它允许我们在光子发射后跟踪轨迹的命运。这意味着我们可以描述稳定分子的振转状态。使用半经典量子化，我们可以获得辐射缔合过程的量子态分辨截面或发射光谱。计算得到的半经典态分辨谱与量子力学微扰理论的结果吻合较好。此外，我们的表面跳跃模型不仅适用于辐射缔合的描述，还可以用于任何自发发射发生的分子过程的半经典特征描述。
