Penning电离的He/Ne--H$_2^+$/HD$^+$复合物的定量经典弛豫动力学
Quantitative Classical Relaxation Dynamics of Penning-Ionized He/Ne--H$_2^+$/HD$^+$ Complexes
中文总结 AI 辅助
本研究通过准经典轨迹模拟定量再现了Penning电离产生的稀有气体--H$_2^+$/HD$^+$复合物的TKER谱，揭示了振动弛豫通道及转动量子数与初始接近几何的关联。
中文摘要 AI 辅助
Penning电离允许原位生成离子复合物，以启动稀有气体--H$_2^+$/HD$^+$复合物的振动弛豫和解离动力学。随之产生的表征双原子阳离子的平动动能释放（TKER）谱是探测分子间相互作用长程部分的特别灵敏的方法。对Ne--H$_2^+$和Ne--HD$^+$复合物进行准经典轨迹（QCT）模拟得到的TKER分布定量匹配了大多数实验观测特征的位置和相对强度，并且与含时量子模拟相当。具体而言，QCT模拟能够分离来自H$_2^+$/HD$^+$弛豫到不同最终振动状态的信号，例如$(v=2) \ ightarrow (v' = 0/1 )$。轨迹分辨的QCT分析还为TKER分布背后的空间和时间依赖动力学提供了机理解释。稀有气体--H$_2^+$/HD$^+$复合物的寿命与双原子的最终转动量子数$j'$直接相关。低$j'$产物主要与稀有气体原子的初始轴向接近相关，而较高$j'$态的形成则主要源于初始T形接近几何构型。
英文摘要
Penning ionization allows {\it in situ} generation of ionic complexes to launch vibrational relaxation and dissociation dynamics for rare gas--H$_2^+$/HD$^+$ complexes. The ensuing translational kinetic energy release (TKER) spectra characterizing the diatomic cation are a particularly sensitive way to probe the long range part of the intermolecular interactions. TKER distributions from quasi-classical trajectory (QCT) simulations for the Ne--H$_2^+$ and Ne--HD$^+$ complexes quantitatively match measured positions and relative intensities of most experimentally observed features and are also on par with time-dependent quantum simulations. Specifically, the QCT-simulations allow to separate signatures arising from H$_2^+$/HD$^+$ relaxation into different final vibrational states, such as for $(v=2) \rightarrow (v' = 0/1 )$. Trajectory-resolved QCT analysis also provides mechanistic interpretations of the spatial and time-dependent dynamics underlying the TKER distributions. Rare gas--H$_2^+$/HD$^+$ complex lifetimes directly correlate with the final rotational quantum number $j'$ of the diatomic. Low-$j'$ products are associated primarily with an initial axial approach of the rare gas atom, whereas formation of higher-$j'$ states predominantly results from an initial T-shaped approach geometry.
