Accurate ab initio calculations of radiative transition probabilities between the A 3Σ+u, B 3Πg, W 3Δu, B′ 3Σ−u, and C 3Πu states of N2
Accurate ab initio calculations of radiative transition probabilities between the A 3Σ+u, B 3Πg, W 3Δu, B′ 3Σ−u, and C 3Πu states of N2
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准确从头计算 N2 的 A 3Σ+u、B 3Πg、W 3Δu、B′ 3Σ−u 和 C 3Πu 态之间的辐射跃迁概率
DOI：
10.1063/1.447917
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发表时间：
1984
期刊：
影响因子：
--
通讯作者：
E. Reinsch
中科院分区：
文献类型：
--
作者：
H. Werner;J. Kalcher;E. Reinsch
N2最低五重态的势能和电子跃迁矩函数已经从高度相关的多组态-参考CI波函数计算出来。从计算的跃迁矩和RKR势能函数，辐射跃迁几率和寿命已被评估，被认为是在15%以内的准确性。理论寿命为36.7 ns的C3-Hu态是在最近的实验值接近一致。计算得到的B 3 μ g态的寿命从v′=0时的13.4 μs下降到v′=12时的4.82 μs。v′=5到v′=12的值与最近的LIF测量结果吻合得很好。然而，v′=0到v′=4的寿命比大多数以前测量的值要大得多。计算值相对于电子波函数的改进是非常稳定的，这一事实使我们得出结论，实验值太低。经验的B-A系统的过渡时刻函数是…
Potential energy and electronic transition moment functions for the lowest five triplet states of N2 have been calculated from highly correlated multiconfiguration‐reference CI wave functions. From the calculated transition moments and RKR potential energy functions, radiative transition probabilities and lifetimes have been evaluated which are believed to be accurate within 15%. The theoretical lifetime of 36.7 ns of the C 3Πu state is in close agreement with the most recent experimental values. The calculated lifetimes of the B 3Πg state decrease from 13.4 μs for v′=0 to 4.82 μs for v′=12. The values for v′=5 to v′=12 are in good agreement with recent LIF measurements. The lifetimes for v′=0 to v′=4, however, are considerably larger than most previously measured values. The fact that the calculated values are very stable with respect to improvements of the electronic wave functions leads us to conclude that the experimental values are too low. Empirical transition moment functions for the B–A system are...