title: Extrapolating Single Organic Ion Solvation Thermochemistry from Simulated Water Nanodroplets.
abstract: We compute the ion/water interaction energies of methylated ammonium cations and alkylated carboxylate anions solvated in large nanodroplets of 10 000 water molecules using 10 ns molecular dynamics simulations and an all-atom polarizable force-field approach. Together with our earlier results concerning the solvation of these organic ions in nanodroplets whose molecular sizes range from 50 to 1000, these new data allow us to discuss the reliability of extrapolating absolute single-ion bulk solvation energies from small ion/water droplets using common power-law functions of cluster size. We show that reliable estimates of these energies can be extrapolated from a small data set comprising the results of three droplets whose sizes are between 100 and 1000 using a basic power-law function of droplet size. This agrees with an earlier conclusion drawn from a model built within the mean spherical framework and paves the road toward a theoretical protocol to systematically compute the solvation energies of complex organic ions.
authors.affiliation: Exascale Computing Research Lab , Campus Teratec, 2 rue de la Piquetterie, 91680 Bruyères-le-Châtel, France.|Université de Versailles Saint-Quentin-en-Yvelines , 55 avenue de Paris, 78000 Versailles, France.
authors.forename: Jonathan P
authors.initials: JP
authors.lastname: Coles
authors.affiliation: CTP - Centre Thermodynamique des Procédés, MINES ParisTech, PSL Research University , 35 rue Saint-Honoré, 77300 Fontainebleau, France.
authors.forename: Céline
authors.initials: C
authors.lastname: Houriez
authors.affiliation: Department of Chemistry, Virginia Commonwealth University , Richmond, Virginia 23284-2006, United States.|Department of Chemistry, University of Canterbury , Christchurch 8001, New Zealand.
authors.forename: Michael
authors.initials: M
authors.lastname: Meot-Ner Mautner
authors.affiliation: Laboratoire de Biologie Structurale et Radiobiologie, Service de Bioénergétique, Biologie Structurale et Mécanismes, Institut de Biologie et de Technologies de Saclay , CEA Saclay, F-91191 Gif-sur-Yvette Cedex, France.
authors.forename: Michel
authors.initials: M
authors.lastname: Masella