同位素N₂中3ppi u c1Pi u（v = 2）里德堡复合体成员的相互作用

Interactions of the 3ppi u c1Pi u(v=2) Rydberg-complex member in isotopic N2.

作者信息

Vieitez M O, Ivanov T I, de Lange C A, Ubachs W, Heays A N, Lewis B R, Stark G

机构信息

Department of Physics and Astronomy, Laser Centre, Vrije Universiteit, De Boelelaan 1081, 1081 HV Amsterdam, The Netherlands.

出版信息

J Chem Phys. 2008 Apr 7;128(13):134313. doi: 10.1063/1.2883955.

DOI:10.1063/1.2883955

PMID:18397070

Abstract

The 3ppi u c1Pi u-X 1Sigmag+(2,0) Rydberg and b' 1Sigmau+-X 1Sigmag+(7,0) valence transitions of 14N2, 14N15N, and 15N2 are studied using laser-based 1 extreme ultraviolet (XUV)+1' UV two-photon-ionization spectroscopy, supplemented by synchrotron-based hotoabsorption measurements in the case of 14N2. For each isotopomer, effective rotational interactions between the c(v=2) and b'(v=7) levels are found to cause strong Lambda-doubling in c(v=2) and dramatic P/R-branch intensity anomalies in the b'-X(7,0) band due to the effects of quantum interference. Local perturbations in energy and predissociation line width for the c(v=2) Rydberg level are observed and attributed to a spin-orbit interaction with the crossing, short-lived C 3Pi u(v=17) valence level.

摘要

利用基于激光的1极紫外（XUV）+1'紫外双光子电离光谱法研究了(^{14}N_2)、(^{14}N^{15}N)和(^{15}N_2)的(3\pi_{i}u - X ^{1}\Sigma_{g}^{+}(2,0))里德堡跃迁以及(b' ^{1}\Sigma_{u}^{+}-X ^{1}\Sigma_{g}^{+}(7,0))价态跃迁，对于(^{14}N_2)的情况，还辅以基于同步加速器的光吸收测量。对于每种同位素异构体，发现(c(v = 2))和(b'(v = 7))能级之间的有效转动相互作用会由于量子干涉效应导致(c(v = 2))中强烈的Λ-双重分裂以及(b'-X(7,0))带中显著的(P/R)分支强度异常。观察到(c(v = 2))里德堡能级的能量局部微扰和预解离线宽，并将其归因于与交叉的、寿命较短的(C ^{3}\Pi_{u}(v = 17))价态能级的自旋-轨道相互作用。