Decay dynamics of the long-range H¯Σg+1 state of D2 and H2: Experiment and theory
Decay dynamics of the long-range H¯Σg+1 state of D2 and H2: Experiment and theory
复制标题
D2 和 H2 的长程 H́Σg+1 态的衰变动力学：实验与理论
DOI：
10.1063/1.2264331
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发表时间：
2006
期刊：
影响因子：
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通讯作者：
K. Tsukiyama
中科院分区：
文献类型：
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作者：
S. Ross;T. Yoshinari;Y. Ogi;K. Tsukiyama
我们提出了D2和H2的远程H¯Σg+1状态的旋转振动能级寿命的精确实验测量，直接从这些激发能级的荧光随时间衰减的观察中获得。这些结果改进和扩展了Reinhold等人的结果。化学。物理学报，2003,17(2):559 - 564。几种衰变途径对这些水平开放，包括荧光，预解离和自电离。我们给出了这些过程的理论结果，每个过程都使用最简单但仍然适当的理论水平进行计算。特别是，理论计算提供了观测寿命的显著振动依赖性的定量解释，以及在H¯势阱内定位良好的能级的寿命的同位素依赖性，因此不受显著隧穿的影响，并深入了解了增强隧穿在自电离中的作用。在这些计算中，H¯…
We present accurate experimental measurements of the lifetimes of rovibrational levels of the long-range H¯Σg+1 state for both D2 and H2, obtained directly from the observation of the time-dependent decay of the fluorescence from these excited levels. These results improve upon and extend those of Reinhold et al. [J. Chem. Phys. 112, 10754 (2000)]. Several decay pathways are open to these levels including fluorescence, predissociation, and autoionization. We present theoretical results for each of these processes, each calculated using the simplest but still appropriate level of theory. In particular, the theoretical calculations provide a quantitative explanation of the dramatic vibrational dependence of the observed lifetimes, the isotope dependence of the lifetimes for levels well localized within the H¯ potential well and therefore not subject to significant tunneling, and an insight into the role of enhanced tunneling in autoionization. In these calculations each of the rovibrational levels of the H¯...