title: Finite temperature properties of clusters by replica exchange metadynamics: the water nonamer.
abstract: We introduce an approach for the accurate calculation of thermal properties of classical nanoclusters. On the basis of a recently developed enhanced sampling technique, replica exchange metadynamics, the method yields the true free energy of each relevant cluster structure, directly sampling its basin and measuring its occupancy in full equilibrium. All entropy sources, whether vibrational, rotational anharmonic, or especially configurational, the latter often forgotten in many cluster studies, are automatically included. For the present demonstration, we choose the water nonamer (H(2)O)(9), an extremely simple cluster, which nonetheless displays a sufficient complexity and interesting physics in its relevant structure spectrum. Within a standard TIP4P potential description of water, we find that the nonamer second relevant structure possesses a higher configurational entropy than the first, so that the two free energies surprisingly cross for increasing temperature.
authors.affiliation: Key Laboratory for Computational Physical Sciences (MOE), Fudan University, Shanghai, China.
authors.forename: Yingteng
authors.initials: Y
authors.lastname: Zhai
authors.forename: Alessandro
authors.initials: A
authors.lastname: Laio
authors.forename: Erio
authors.initials: E
authors.lastname: Tosatti
authors.forename: Xin-Gao
authors.initials: XG
authors.lastname: Gong
mesh_terms: D049329:Nanostructures / Q000737:chemistry*; D013816:Thermodynamics; D014867:Water / Q000737:chemistry*
chemical_list: D014867:Water