Regional Centre of Advanced Technologies and Materials, Department of Physical Chemistry, Faculty of Science, Palacký University, Olomouc, Czech Republic.
J Chem Phys. 2011 Feb 28;134(8):084305. doi: 10.1063/1.3555275.
The photodissociation dynamics of the argon ionized trimer Ar(3)(+) is revisited in the light of recent experimental results of Lepère et al. [J. Chem. Phys. 134, 194301 (2009)], which show that the fragment with little kinetic energy is always a neutral one, thus the available energy is shared by a neutral and ionic fragments as in Ar(2)(+). We show that these results can be interpreted as the photodissociation of the linear isomer of the system. We perform a 3D quantum computation of the vibrational spectrum of the system and study the relative populations of the linear (trimer-core) and perpendicular (dimer-core) isomers. We then show that the charge initially located on the central atom in the ground electronic state of the linear isomer migrates toward the extreme ones in the photoexcitation process such that photodissociation of the linear isomer produces a neutral central atom at rest in agreement with measured product state distributions.
氩三离子（Ar(3)(+)）的光解离动力学在 Lepère 等人的最新实验结果[J. Chem. Phys. 134, 194301 (2009)]的基础上进行了重新研究，该结果表明具有少量动力学能量的碎片总是中性的，因此可用能量在中性和离子碎片之间共享，就像在 Ar(2)(+)中一样。我们表明，这些结果可以解释为系统的线性异构体的光解。我们对系统的振动光谱进行了 3D 量子计算，并研究了线性（三核核心）和垂直（二核核心）异构体的相对丰度。然后，我们表明，在光激发过程中，最初位于线性异构体基态中心原子上的电荷会向极端原子迁移，从而使得线性异构体的光解产生一个静止的中性中心原子，这与测量的产物态分布一致。
