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Statisticodynamical approach of final state distributions in associative desorptions

机译:缔合解吸中最终状态分布的统计动力学方法

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In associative desorptions governed by short-range forces,strong energy transfers between rotational,translational,and vibrational degrees of freedom of the nascent molecule take place beyond the transition state (TS).State or energy distributions are thus different at the TS and in the vacuum.Inspired by previous studies on unimolecular reactions,a Statisticodynamical approach (SDA) is proposed which combines the transition state theory for the description of state distributions at the TS and a simple dynamical model to account for the effect of the post-TS dynamics on these distributions.The agreement found between the predictions of SDA,the much more demanding classical trajectory calculations,and experimental results in the case of H_2 and D_2 desorbing from Cu(111) is very satisfying.In addition to that,the formulation highlights some key factors of state distributions which would have been difficult to directly extract from a dynamical study.The notions of vibrational heating and rotational cooling are discussed within this context.
机译:在由短程力控制的缔合解吸中,新生分子的旋转,平移和振动自由度之间的强能量转移发生在过渡态(TS)之外,因此在TS和受先前关于单分子反应的研究的启发,提出了一种统计动力学方法(SDA),该方法将过渡状态理论用于描述TS处的状态分布,并结合了一个简单的动力学模型来考虑TS后动力学对结构的影响。在SDA的预测,更苛刻的经典轨迹计算之间以及在H_2和D_2从Cu(111)中解吸的实验结果之间的一致性非常令人满意。此外,该公式突出了一些关键难以直接从动力学研究中提取的状态分布的因素。在此讨论旋转冷却。

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