Free energy decomposition analysis of bonding and nonbonding interactions in solution

Abstract

A free energy decomposition analysis algorithm for bonding and nonbonding interactions in various solvated environments, named energy decomposition analysis-polarizable continuum model (EDA-PCM), is implemented based on the localized molecular orbital-energy decomposition analysis (LMO-EDA) method, which is recently developed for interaction analysis in gas phase [P. F. Su and H. Li, J. Chem. Phys. 130, 074109 (2009)]. For single determinant wave functions, the EDA-PCM method divides the interaction energy into electrostatic, exchange, repulsion, polarization, desolvation, and dispersion terms. In the EDA-PCM scheme, the homogeneous solvated environment can be treated by the integral equation formulation of PCM (IEFPCM) or conductor-like polarizable continuum model (CPCM) method, while the heterogeneous solvated environment is handled by the Het-CPCM method. The EDA-PCM is able to obtain physically meaningful interaction analysis in different dielectric environments along the whole potential energy surfaces. Test calculations by MP2 and DFT functionals with homogeneous and heterogeneous solvation, involving hydrogen bonding, vdW interaction, metal-ligand binding, cation-π, and ionic interaction, show the robustness and adaptability of the EDA-PCM method. The computational results stress the importance of solvation effects to the intermolecular interactions in solvated environments.