Spin-Polarized Rb2 Interacting with Bosonic He Atoms: Potential Energy Surface and Quantum Structures of Small Clusters

• Published in: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Molecules, spectroscopy, kinetics, environment, & general theory, 2012-03, Vol.116 (10), p.2394-2404
• Main Authors: Rodríguez-Cantano, R, López-Durán, David, González-Lezana, T, Delgado-Barrio, G, Villarreal, P, Yurtsever, E, Gianturco, F. A
• Format: Article
• Language: English
• ISSN: 1089-5639; 1520-5215
• DOI: 10.1021/jp3004932

A new full-dimension potential energy surface of the three-body He–Rb2(3Σ u +) complex and a quantum study of small (4He) N –Rb2(3Σ u +) clusters, 1 ≤ N ≤ 4, are presented. We have accurately fitted the ab initio points of the interaction to an analytical form and addressed the dopant’s vibration, which is found to be negligible. A Variational approach and a Diffusion Monte Carlo technique have been applied to yield energy and geometric properties of the selected species. Our quantum structure calculations show a transition in the arrangements of the helium atoms from N = 2, where they tend to be separated across the diatomic bond, to N = 4, in which a closer packing of the rare gas particles is reached, guided by the dominance of the He–He potential over the weaker interaction of the latter adatoms with the doping dimer. The deepest well of the He–Rb2 interaction is placed at the T-shape configuration, a feature which causes the dopant to be located as parallel to the helium “minidroplet”. Our results are shown to agree with previous findings on this and on similar systems.