Laboratoire de Physique Moléculaire pour l'Atmosphère et l'Astrophysique, Université Pierre et Marie Curie, 4 place Jussieu, 75252 Paris Cedex 05, France.
J Phys Chem A. 2009 Nov 26;113(47):13124-32. doi: 10.1021/jp902846c.
The positions and intensities of the Q(N) (N = 1-4) X1 Sigma(g)+ --> nppi1 Pi(u)- (n = 2 to approximately 30) absorption transitions of H2 have been calculated by multichannel quantum defect theory. The computations are based on the quantum chemical ab initio clamped nuclei potential curves and absorption dipole transition moments for n = 2-4 of Wolniewicz and Staszewska (J. Mol. Spectrosc. 2003, 220, 45). The resulting Einstein spontaneous Einstein A coefficients are in good agreement with those derived from the absolute intensity measurements of Glass-Maujean et al. (Mol. Phys. 2007, 105, 1535). The results reveal widespread vibronic intensity perturbations in the Q(N) Rydberg series, whereas the line frequencies are comparatively little affected by nonadiabatic effects.
通过多通道量子亏损理论，我们计算了 H2 的 Q（N）（N = 1-4）X1 Sigma（g）+ → nppi1 Pi（u）-（n = 2 到约 30）吸收跃迁的位置和强度。这些计算基于 Wolniewicz 和 Staszewska（J. Mol. Spectrosc. 2003, 220, 45）的量子化学从头算固定核势曲线和 n = 2-4 的吸收偶极跃迁矩。由此得出的爱因斯坦自发爱因斯坦 A 系数与 Glass-Maujean 等人（Mol. Phys. 2007, 105, 1535）的绝对强度测量得出的结果非常吻合。结果表明，Q（N）里德堡系列存在广泛的振子强度微扰，而线频率受非绝热效应的影响相对较小。
