Leiden Institute of Chemistry, Gorlaeus Laboratories, Leiden University, P.O. Box 9502, 2300 RA Leiden, The Netherlands.
J Chem Phys. 2009 Nov 21;131(19):194303. doi: 10.1063/1.3263605.
The 3D photodissociation dynamics of HCl and HF molecules adsorbed on ice is studied by quantum and classical simulations. The quantum calculations are carried out with the multiconfiguration time-dependent Hartree (MCTDH) approach. Dynamical observables like angular distributions in the momentum space of the H fragments, absorption cross sections are computed. The results are compared with our previous 2D studies. As expected, less encapsulation of the H atom between the ice surface and the halogen atom is obtained in the 3D study, resulting in less pronounced interference structures in the photoabsorption cross sections and in a decrease of the classical rainbow peaks observed in the 2D scheme. Although the amplitudes of the oscillations corresponding to quantum interferences in the asymptotic angular distribution of the H fragment are different between the 2D and 3D results, the qualitative pattern of the oscillations is similar in the 2D and 3D approaches. In addition, a good agreement is observed for the angular distribution between the classical and the quantum calculations.
通过量子和经典模拟研究了吸附在冰上的 HCl 和 HF 分子的 3D 光解动力学。量子计算采用多组态含时哈特ree（MCTDH）方法进行。计算了 H 碎片动量空间中的角分布等动力学观测值，吸收截面。将结果与我们之前的 2D 研究进行了比较。正如预期的那样，在 3D 研究中，H 原子在冰表面和卤素原子之间的包裹较少，导致光吸收截面中的干涉结构不那么明显，并且在 2D 方案中观察到的经典彩虹峰减少。尽管 2D 和 3D 结果中对应于 H 碎片渐近角分布中量子干涉的振荡幅度不同，但振荡的定性模式在 2D 和 3D 方法中是相似的。此外，在经典和量子计算之间的角分布上观察到了很好的一致性。
