HeICl络合物的振动预离解:含时黄金规则波包研究

VIBRATIONAL PREDISSOCIATION OF THE HeICl COMPLEX: A TIME DEPENDENT GOLDEN RULE WAVE PACKET STUDY

用含时黄金规则波包法计算了ＨｅＩＣｌｖａｎｄｅｒＷａａｌｓ络合物分子的振动预离解寿命和离解碎片ＩＣｌ的终转动态分布。并与实验和其他理论计算结果做了比较。波包计算所用的总传播时间（不超过１ｐｓ，远小于离解寿命）实际上是解离碎片在振动退激发绝热势能面上的滞留时间。终态相互作用对终转动态分布起着决定性作用。并预言了ＨｅＩＣｌ终转动态分布对振动态的依赖。

We have carried out three dimensional, time dependent golden rule wave packet calculations of vibrational predissociation of the van der Waals HeICl comples. Computed lifetimes and the final rotational distributions from the lowest van der Waals level with total angular momentum j=0 are in good agreement with experiment and the time dependent quantum calculation, where available. calculated final rotational distributions display the broad bimodality, as experimentally observed. The propagation time needed in the golden rule wave packet calculation for vibrational predissociation does not correspond to the lifetime of the predissociation state. Rather, it is the time of final state interaction or the dwelling time on the vibrationally deexcited adiabatic ν-1 potential energy surface before the fragments separator from each other. This time is generally expected to be much shorter than the predissociation lifetime of the molecule. The results show that the final interaction between the fragments plays a predominant role in determining the final rotational distributions. It is also predicted that the final rotational distributions of HeICl complex are dependent on its initial vibrational state.