title: Ab initio investigation of the aqueous solvation of the nitrate ion.
abstract: The surface affinity of the nitrate ion in aqueous clusters is investigated with a variety of theoretical methods. A sampling of structures in which the nitrate ion is solvated by 32 water molecules is optimized using second order Møller-Plesset perturbation theory (MP2). Four of these MP2 optimized structures are used as starting points for fully ab initio molecular dynamics simulations at the dispersion corrected restricted Hartree-Fock (RHF-D) level of theory. The nitrate ion solvated by 16, 32, and 64 water molecules is also investigated with umbrella sampling molecular dynamics simulations using QM/MM methodology, where the nitrate ion is modeled with MP2 and the water molecules are described using either the non-empirical effective fragment potential (EFP) or the empirical TIP5P potential. The turning point between surface and interior solvation of the nitrate ion is predicted to lie around a cluster size of 64 water molecules.
authors.affiliation: Argonne Leadership Computing Facility, Argonne, Illinois 60439, USA. spruitt@anl.gov.
authors.forename: Spencer R
authors.initials: SR
authors.lastname: Pruitt
authors.forename: Kurt R
authors.initials: KR
authors.lastname: Brorsen
authors.forename: Mark S
authors.initials: MS
authors.lastname: Gordon
mesh_terms: D007477:Ions / Q000737:chemistry; D056004:Molecular Dynamics Simulation; D009566:Nitrates / Q000737:chemistry*; D011789:Quantum Theory; D012995:Solubility; D014867:Water / Q000737:chemistry*
chemical_list: D007477:Ions; D009566:Nitrates; D014867:Water