Comparison of three effective Hamiltonian models of increasing complexity: Triazene in water as a test case

Abstract

A critical comparison of widely used solvation models is reported. It is illustrated by a study of the triazene molecule in liquid water. We consider the following approaches: (1) a continuum model based on multicentric multipole expansions of the charge distribution, (2) the averaged solvent electrostatic potential from molecular dynamics (ASEP/MD) method, and (3) molecular dynamics simulations using a combined quantum mechanics/molecular mechanics potential (QM/MM/MD). We find that the solvation induces appreciable changes in the geometry and charge distribution of triazene. These changes are only qualitatively reproduced by the dielectric continuum model, which clearly underestimates induced dipole moments and solute-solvent interaction energy. We also show that the use of effective point charges placed on solute nuclei during the classical simulations may cause significant errors in the description of the solvent structure. The addition of charges representing nitrogen atom lone pairs is compulsory to reproduce the QM/MM/MD simulation results. Moreover, our results validate the use of the mean field approximation in the study of solvent effects. A major conclusion of this study is that the ASEP/MD method constitutes a reliable alternative to the much more computationally demanding QM/MM/MD methods.