多原子光解离的半经典统计动力学描述：态分辨分布
Semiclassical statistico-dynamical description of polyatomic photo-dissociations: State-resolved distributions
摘要：
本文提出了一种研究间接多原子准经典轨道过程的新方法，该方法在提供振转分辨的同时，有效地避免了任何分级或加权过程。初始经典态以角度作用变量开始，以紧密匹配量子实验条件，然后按照最近发表的算法[J. Chem. Phys. 130，114103（2009）]转换为笛卡尔坐标。然后使用“关联”图传播轨迹，即在Hamilton和Brumer [J.Chem.Phys.82，595（1985）]的出口通道校正相空间理论的精神下的逆动力学模拟，这被证明是特别方便的。最后，提供了一个近似的准经典公式，在一般条件下，可以用来添加可能的旋转结构的振动分辨准经典分布。为了介绍该方法并说明其能力，研究了来自最近在308 nm处烯酮的光解离实验的相关平移能量分布[J. Chem. Phys. 124，014303（2006）]。一般来说，整体理论算法减少了要整合的轨迹总数，并允许对多原子实验进行完全理论预测。
英文摘要：
An alternative methodology to investigate indirect polyatomic processes with quasi-classical trajectories is proposed, which effectively avoids any binning or weighting procedure while provides rovibrational resolution. Initial classical states are started in terms of angle-action variables to closely match the quantum experimental conditions and later transformed into Cartesian coordinates, following an algorithm very recently published [J. Chem. Phys. 130, 114103 (2009)]. Trajectories are then propagated using the 'association' picture, i.e. an inverse dynamics simulation in the spirit of the exit-channel corrected phase space theory of Hamilton and Brumer [J. Chem. Phys. 82, 595 (1985)], which is shown to be particularly convenient. Finally, an approximate quasi-classical formula is provided which under general conditions can be used to add possible rotational structures into the vibrationally-resolved quasi-classical distributions. To introduce the method and illustrate its capabilities, correlated translational energy distributions from recent experiments in the photo-dissociation of ketene at 308 nm [J. Chem. Phys. 124, 014303 (2006)] are investigated. Quite generally, the overall theoretical algorithm reduces the total number of trajectories to integrate and allows for fully theoretical predictions of experiments on polyatomics.
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