Electronically excited rubidium atom in helium clusters and films. II. Second excited state and absorption spectrum.
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.
Institut de Physique de Rennes, UMR 6251, CNRS & Université de Rennes 1, F-35042 Rennes, France.
Markku
M
Leino
Alexandra
A
Viel
Robert E
RE
Zillich
D000465:Algorithms; D004058:Diffusion; D004583:Electrons; D006371:Helium / Q000737:chemistry*; D008567:Membranes, Artificial; D009010:Monte Carlo Method; D011789:Quantum Theory; D012413:Rubidium / Q000737:chemistry*; D013056:Spectrophotometry, Ultraviolet; D013499:Surface Properties
D008567:Membranes, Artificial; D006371:Helium; D012413:Rubidium