Janecek Ivan, Hrivnák Daniel, Kalus René, Gadéa Florent Xavier
Department of Physics, University of Ostrava, 30. dubna 22, 701 03 Ostrava, Czech Republic.
J Chem Phys. 2006 Sep 14;125(10):104315. doi: 10.1063/1.2337632.
The dynamics of ionic rare-gas trimers (Ar(3) (+), Kr(3) (+), and Xe(3) (+)) produced by a sudden ionization of neutral precursors is investigated theoretically with a hybrid classical-quantum method for solving the equations of motion governed by a Hamiltonian obtained from a previously tested diatomics-in-molecules model. Initial conditions are selected with Monte Carlo sampling. Two possibilities for generating the initial electronic state are considered: diabatic (local) and adiabatic (delocalized). The dynamics generally leads to fragmentation, producing either monomer ions or dimer ions in a relatively short time; however, a large number of long-lived metastable trimer ions are also seen in some cases. We have analyzed the dynamics with respect to the fraction of monomer ions produced, the distribution of the kinetic energy of the products, and the distribution of fragmentation times of the trimers. Initial diabatic ionization is associated with much faster fragmentation than adiabatic ionization. Spin-orbit coupling plays an important role in the fragmentation dynamics.
采用混合经典-量子方法，从先前经过测试的分子中的双原子模型得到哈密顿量，进而求解运动方程，对中性前驱体突然电离产生的离子型稀有气体三聚体（Ar(3) (+)、Kr(3) (+) 和 Xe(3) (+)）的动力学进行了理论研究。通过蒙特卡罗采样选择初始条件。考虑了产生初始电子态的两种可能性：非绝热（局域）和绝热（离域）。动力学过程通常会导致碎片化，在相对较短的时间内产生单体离子或二聚体离子；然而，在某些情况下也会出现大量长寿命的亚稳三聚体离子。我们针对产生的单体离子分数、产物动能分布以及三聚体碎片化时间分布对动力学进行了分析。初始非绝热电离比绝热电离的碎片化速度快得多。自旋-轨道耦合在碎片化动力学中起着重要作用。
