Electronically excited rubidium atom in helium clusters and films. II. Second excited state and absorption spectrum

Markku Leino (1) , Alexandra Viel (1) , Robert E. Zillich (2)

1 IPR - Institut de Physique de Rennes
2 Institute for Theoretical Physics

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.

Mots clés: Quantum dynamics; Helium clusters; Quantum Monte Carlo; Molecular physics

Domaines: Physique Atomique [physics.atom-ph]; Chimie théorique et/ou physique; Physique [physics]

Markku Leino, Alexandra Viel, Robert E. Zillich. Electronically excited rubidium atom in helium clusters and films. II. Second excited state and absorption spectrum. Journal of Chemical Physics, 2011, 134 (2), pp.024316. ⟨10.1063/1.3528936⟩. ⟨hal-00711625⟩