An effective fragment method for modeling solvent effects in quantum mechanical calculations

Abstract

An effective fragment model is developed to treat solvent effects on chemical properties and reactions. The solvent, which might consist of discrete water molecules, protein, or other material, is treated explicitly using a model potential that incorporates electrostatics, polarization, and exchange repulsion effects. The solute, which one can most generally envision as including some number of solvent molecules as well, is treated in a fully ab initio manner, using an appropriate level of electronic structure theory. In addition to the fragment model itself, formulae are presented that permit the determination of analytic energy gradients and, therefore, numerically determined energy second derivatives (hessians) for the complete system. Initial tests of the model for the water dimer and water‐formamide are in good agreement with fully ab initio calculations.