Br2(X) microsolvation in helium clusters: effect of the interaction on the quantum solvent density distribution.
The Born-Oppenheimer potential energy surface for the Br2(X) molecule interacting with a varying number of 4He bosons is constructed following two different schemes which employ either a full ab initio evaluation of the Br2-He interaction forces or an estimate of the latter through an empirical model. Both descriptions are employed by carrying out diffusion Monte Carlo (DMC) calculations of the ground-state energies and quantum wavefunctions for Br2-(He)n clusters with n up to 24. The results clearly indicate, for both interactions, the occurrence of the full solvation of the molecular dopant within the quantum bosonic "solvent" but also show differences between the two models in terms of the expected density distributions of the surrounding particles within the shorter-range region that makes up the clusters with smaller n values. Our calculations also show that such differences become insignificant for the larger 4He clusters surrounding the Br2 molecule, where density profiles and bulk behaviour are chiefly driven by the solvent structure, once n values reach the region of 15-20 adatoms.
Di Paola
Cono
C
Department of Chemistry and INFM, University of Rome, La Sapienza, Piazzale A. Moro 5, 00185 Rome, Italy.
Gianturco
Franco A
FA
López-Durán
David
D
de Lara-Castells
Maria Pilar
MP
Delgado-Barrio
Gerardo
G
Villarreal
Pablo
P
Jellinek
Julius
J