Structuring a quantum solvent around a weakly bound dopant: the He-Cs2((3)sigma u) complex

Abstract

The structure and energetics of 3,4HeCs2(3Σu) molecules are analyzed from first principles. Fixing the cesium dimer at its equilibrium distance, the electronic structure was determined through ab initio methods at the CCSD(T) level of theory using a large basis set to compute the interaction energies. At the T-shaped geometry, there is a shallow well with a depth of ∼2 cm−1 placed at R ∼6.75 Å, R being the distance from the center of mass of Cs2 to He. That depth gradually decreases to ∼0.75 cm−1, while R increases to about 11.5 Å at linear arrangements. A simple model of adding atom−atom Lennard-Jones potentials with well-depth and equilibrium distance parameters depending on the angular orientation was found to accurately reproduce the ab initio points. Using this analytical form, variational calculations at zero total angular momentum are performed, predicting a single bound level at ∼−0.106 (∼−0.042) cm−1 for the boson (fermion) species. Further calculations using Quantum Monte Carlo methods are carried out and found to be in good agreement with the variational ones. On the basis of the present results, such analytical expression could in turn be used to describe the structure and binding of larger complexes and therefore opens the possibility to further studies involving such aggregates.