Ar ··· I 2 : A model system for complex dynamics
Ar ··· I 2 : A model system for complex dynamics
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Ar... I 2：复杂动力学模型系统
DOI：
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发表时间：
2003
期刊：
影响因子：
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通讯作者：
O. Roncero
中科院分区：
文献类型：
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作者：
A. Buchachenko;N. Halberstadt;B. Lepetit;O. Roncero
本文综述了Ar···I2范德华络合物B-L X跃迁的光谱和光解动力学研究，包括态的离解极限以下和以上。这个非常简单的系统构成了一个广泛的分子过程的原型：包括分子内振动弛豫的振动预解离，电子预解离，笼子效应，…。这些过程中的每一个都已经或仍然是不同解释的主题：参与该系统振动预解离的分子内振动弛豫可以是稀疏的或统计的，振动和电子预解离是竞争的，并且已经提出了对笼效应的直接的弹道解释以及非绝热的解释。通过两个稳定的Ar(···I2)异构体的共存，研究了这些动力学过程对络合物(立体动力学)两个配对的相对取向的依赖关系。对实验和理论结果进行了综述。实验范围从频率分辨研究到时间依赖研究，包括确定最终状态分布。理论研究包括络合物的几个电子态及其耦合的势能面计算，以及绝热和非绝热动力学模拟。
We review spectroscopic and photodissociation dynamical studies in the region of the B L X transition of the Ar ··· I 2 van der Waals complex, both below and above the dissociation limit of the state. This very simple system constitutes a prototype for a wide range of molecular processes: vibrational predissociation involving intramolecular vibrational relaxation, electronic predissociation, cage effect, …. Each of these processes has been or still is the subject of differing interpretations: intramolecular vibrational relaxation involved in the vibrational predissociation of this system can be in the sparse or statistical regime, vibrational and electronic predissociation are in competition and a direct, ballistic interpretation of the cage effect as well as a non-adiabatic one have been proposed. The study of the dependence of these dynamical processes on the relative orientation of the two partners of the complex (stereodynamics) is made possible by the coexistence of two stable Ar ··· I 2 ) isomers. Experimental as well as theoretical results are reviewed. Experiments range from frequency-resolved to time-dependent studies, including the determination of final state distributions. Theoretical studies involve potential energy surface calculations for several electronic states of the complex and their couplings and adiabatic as well as non-adiabatic dynamical simulations.