Laboratoire Aimé Cotton du CNRS, Bâtiment 505, Université de Paris-Sud, F91405 Orsay, France.
J Chem Phys. 2010 Dec 7;133(21):214303. doi: 10.1063/1.3518039.
Indirect dissociative recombination of low-energy electrons and molecular ions often occurs through capture into vibrationally excited Rydberg states. Properties of vibrational autoionization, the inverse of this capture mechanism, are used to develop some general ideas about the indirect recombination process, and these ideas are illustrated by examples from the literature. In particular, the Δv = -1 propensity rule for vibrational autoionization, i.e., that vibrational autoionization occurs by the minimum energetically allowed change in vibrational quantum numbers, leads to the prediction of thresholds in the dissociative recombination cross sections and rates at the corresponding vibrational thresholds. Capture into rotationally excited Rydberg states is also discussed in terms of recent low-temperature studies of the dissociative recombination of H(3)(+).
低能电子与分子离子的间接离解复合通常通过捕获到振动激发的里德堡态来实现。振动自电离的性质（这种捕获机制的逆过程）被用来发展一些关于间接复合过程的一般想法，并且这些想法通过文献中的例子来说明。特别是，振动自电离的Δv=-1 倾向规则，即振动自电离通过振动量子数的最小能量允许变化发生，导致在相应的振动阈值处预测离解复合截面和速率的阈值。根据最近对 H(3)(+)的离解复合的低温研究，也讨论了捕获到转动激发的里德堡态的情况。
