Institut de Physique de Rennes, UMR 6251, CNRS & Université de Rennes 1, F-35042 Rennes, France.
J Chem Phys. 2011 Jan 14;134(2):024316. doi: 10.1063/1.3528936.
Following our work on the study of helium droplets and film doped with one electronically excited rubidium atom Rb(∗) ((2)P) [M. Leino, A. Viel, and R. E. Zillich, J. Chem. Phys. 129, 184308 (2008)], we focus in this paper on the second excited state. We present theoretical studies of such droplets and films using quantum Monte Carlo approaches. Diffusion and path integral Monte Carlo algorithms combined with a diatomics-in-molecule scheme to model the nonpair additive potential energy surface are used to investigate the energetics and the structure of Rb(∗)He(n) clusters. Helium films as a model for the limit of large clusters are also considered. As in our work on the first electronic excited state, our present calculations find stable Rb(∗)He(n) clusters. The structures obtained are however different with a He-Rb(∗)-He exciplex core to which more helium atoms are weakly attached, preferentially on one end of the core exciplex. The electronic absorption spectrum is also presented for increasing cluster sizes as well as for the film.
继我们对氦液滴和掺杂一个电子激发铷原子 Rb(∗) ((2)P) 的薄膜的研究之后[M. Leino、A. Viel 和 R. E. Zillich，J. Chem. Phys. 129, 184308 (2008)]，我们在本文中重点研究了第二激发态。我们使用量子蒙特卡罗方法对这些液滴和薄膜进行了理论研究。扩散和路径积分蒙特卡罗算法与双原子分子方案相结合，用于模拟非对加势能面，以研究 Rb(∗)He(n)团簇的能量和结构。我们还考虑了氦膜作为大团簇极限的模型。与我们在第一电子激发态的工作一样，我们目前的计算发现了稳定的 Rb(∗)He(n)团簇。然而，得到的结构不同，具有 He-Rb(∗)-He 激基复合物的核心，更多的氦原子较弱地附着在复合物核心的一端。还给出了随着团簇尺寸增加以及薄膜的电子吸收光谱。
