How accurate is the SMD model for predicting free energy barriers for nucleophilic substitution reactions in polar protic and dipolar aprotic solvents?

Abstract

In the past seven years, the SMD (Solvent Model Density) method has been widely used by computational chemists. Thus, assessment on the reliability of this model for modeling chemical process in solution is worthwhile. In this report, it was investigated six anion-molecule nucleophilic substitution reactions in methanol and dipolar aprotic solvents. Geometry optimizations have been done at SMD/X3LYP level and single point energy calculations at CCSD(T)/TZVPP + diff level. Our results have indicated that the SMD model is not adequate for dipolar aprotic solvents, with a root of mean squared (RMS) error of 5.6 kcal mol-1, while the Polarizable Continuum Model (PCM) method with the Pliego and Riveros atomic cavities has led to RMS error of only 3.2 kcal mol-1. For methanol solvent, the SMD method has a RMS error of 3.0 kcal mol-1. The classical protic to dipolar aprotic solvent rate acceleration effect was not predicted by the SMD model for the tested systems.