Institute of Experimental Physics, Graz University of Technology, Petersgasse 16, Graz 8010, Austria.
J Chem Phys. 2010 Feb 7;132(5):054304. doi: 10.1063/1.3308493.
It is well known that alkali-metal molecules are preferentially observed in the weak van der Waals-bound high spin states by helium droplet isolation spectroscopy. In [F. R. Brühl et al., J. Chem. Phys. 115, 10275 (2001)] the Rb(2) (2)(3)Pi(g)-a (3)Sigma(u)(+) band on He droplets was investigated by laser-induced fluorescence and dispersed emission spectroscopy. At that time no information on the magnitude of spin-orbit coupling was available for the (2)(3)Pi(g) state which connects to the atomic 5s+4d asymptote and it was neglected. In this work we reinvestigate the observed spectra. The dispersed emission spectra, which resulted from free molecules, are consistent with state-of-the-art nonrelativistic potential energy surfaces and effective spin-orbit coupling matrix elements obtained from resonance-enhanced multiphoton ionization spectroscopy of cold Rb dimers [J. Lozeille et al., Eur. Phys. J. D 39, 261 (2006)]. Having validated the theoretical description of the free molecule state, we use the laser-induced fluorescence spectrum to discuss the influence of the He droplet on the excitation band.
众所周知，通过氦滴隔离光谱学，碱金属分子优先在弱范德华束缚的高自旋态中被观察到。在[F. R. Brühl 等人，J. Chem. Phys. 115, 10275（2001）]中，通过激光诱导荧光和分散发射光谱研究了 He 滴中的 Rb(2)（2）（3）Pi(g)-a（3）Sigma(u)(+)带。当时，对于连接到原子 5s+4d 渐近线的（2）（3）Pi(g)态，没有关于自旋轨道耦合大小的信息，因此被忽略了。在这项工作中，我们重新研究了观察到的光谱。从自由分子中得到的分散发射光谱与从冷 Rb 二聚体的共振增强多光子电离光谱中获得的最先进的非相对论势能面和有效自旋轨道耦合矩阵元一致[J. Lozeille 等人，Eur. Phys. J. D 39, 261（2006）]。在验证了自由分子态的理论描述之后，我们使用激光诱导荧光光谱来讨论 He 滴对激发带的影响。
