Ab initio investigation of the aqueous solvation of the nitrate ion

作者：Pruitt Spencer R^*; Brorsen Kurt R; Gordon Mark S

来源：Physical Chemistry Chemical Physics, 2015, 17(40): 27027-27034.

DOI：10.1039/c5cp04445f

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 Moller-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.

• 出版日期2015