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Br 2 (X) Microsolvation in Helium Clusters: Effect of the Interaction on the Quantum Solvent Density Distribution
Author(s) -
Di Paola Cono,
Gianturco Franco A.,
LópezDurán David,
de LaraCastells Maria Pilar,
DelgadoBarrio Gerardo,
Villarreal Pablo,
Jellinek Julius
Publication year - 2005
Publication title -
chemphyschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.016
H-Index - 140
eISSN - 1439-7641
pISSN - 1439-4235
DOI - 10.1002/cphc.200400530
Subject(s) - solvation , diffusion monte carlo , quantum monte carlo , chemistry , ab initio , wave function , quantum , ab initio quantum chemistry methods , density functional theory , molecule , atomic physics , helium , solvation shell , monte carlo method , molecular physics , computational chemistry , physics , quantum mechanics , monte carlo molecular modeling , statistics , mathematics , organic chemistry , markov chain monte carlo
The Born–Oppenheimer potential energy surface for the Br 2 (X) molecule interacting with a varying number of 4 He bosons is constructed following two different schemes which employ either a full ab initio evaluation of the Br 2 –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 Br 2 –(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 4 He clusters surrounding the Br 2 molecule, where density profiles and bulk behaviour are chiefly driven by the solvent structure, once n values reach the region of 15–20 adatoms.