title: Diatomics-in-Molecules Modeling of Many-Body Effects on the Structure and Thermodynamics of Mercury Clusters.
abstract: The stable structures and melting behavior of Hgn clusters, 2 ≤ n < 60, have been theoretically investigated using an updated diatomics-in-molecules (DIM) model initially proposed by Kitamura [Chem. Phys. Lett.2006, 425, 2056]. Global optimization and sampling at finite temperature are achieved on the basis of hierarchical and nested Markov chain Monte Carlo methods, respectively. The DIM model predicts highly symmetric icosahedral global minima that are generally similar to the standard van der Waals atomic clusters, without any indication of distorted or low-coordinated geometries, but also at variance with the global minima found with the pairwise Hg2 potential. The combined influences of surface and many-body effects due to s-p mixing are considerable on the melting point: although the model predicts a bulk melting temperature in fair agreement with experimental results, it is found to decrease with increasing cluster size.
authors.affiliation: LASIM, CNRS UMR 5579, Université de Lyon, 43 Bd. du 11 Novembre 1918, F69622 Villeurbanne Cedex, France.
authors.forename: F
authors.initials: F
authors.lastname: Calvo
authors.affiliation: Centre for Theoretical Chemistry and Physics, Institute of Natural Science, Massey University Albany, Private Bag 102904, North Shore City, 0745 Auckland, New Zealand.
authors.forename: E
authors.initials: E
authors.lastname: Pahl
authors.affiliation: Centre for Theoretical Chemistry and Physics, New Zealand Institute for Advanced Study, Massey University Albany, Private Bag 102904, North Shore City, 0745 Auckland, New Zealand and Fachbereich Chemie, Philipps-Universität Marburg, Hans-Meerwein-Str. D35032 Marburg, Germany.
authors.forename: P
authors.initials: P
authors.lastname: Schwerdtfeger
authors.affiliation: LCPQ, CNRS and Université de Toulouse (UPS), 118 Route de Narbonne, F31062 Toulouse Cedex, France.
authors.forename: F
authors.initials: F
authors.lastname: Spiegelman