Quantum Mechanical Modeling of the Interactions between Noble Metal (Ag and Au) Nanoclusters and Water with the Effective Fragment Potential Method.

Explicit solvent interactions can significantly alter the physical and chemical properties of noble metal (e.g., gold and silver) nanoclusters. In order to compute these solvent interactions at a reasonable computational cost, a quantum mechanical (QM)/molecular mechanics (MM) approach, where the metal nanocluster is treated with full QM and the water molecules are treated with a MM force field, can be used. However, classical MM force fields were typically parameterized using molecules containing main group elements as the reference. The accuracy of noble metal-solvent interactions obtained with these force fields therefore remains unpredictable. The effective fragment potential (EFP) force field, designed to model explicitly solvated systems, represents an attractive method to simulate solvated noble metal nanoclusters because it is derived from first principles and contains few or no fitted parameters, depending on implementation. At the density functional theory-optimized geometries, good correlation is obtained between the nanocluster-water interaction energies computed with EFP and those computed with the reference coupled cluster singles, doubles, and perturbative triples method. It is shown that the EFP method gives qualitatively accurate interaction energies at medium-large intermolecular distances for various molecular configurations. In order to achieve higher quantitative accuracy, the first solvation shell should be treated with full QM, if possible. EFP is therefore a promising method for the QM modeling of explicitly solvated silver and gold nanoclusters.