THE SWITCHING/GAUSSIAN METHOD FOR POLARIZABLE CONTINUUM MODELS WITH APPLICATIONS TO AQUEOUS MOLECULAR DYNAMICS AND VIBRATIONAL SPECTRA

Abstract

We describe the recently-developed Switching/Gaussian (SWIG) formalism for polarizable continuum models (PCMs) in electronic structure theory and QM/MM calculations. Existing PCM implementations are well-established, yet still exhibit Coulomb singularities and/or discontinuities in potential energy surfaces, which result from the finite-element discretization of the solute--continuum interface. Our revised implementation eliminates these problems. We illustrate the robustness this approach using \textit{ab initio} molecular dynamics and vibrational spectra calculations, for which existing PCM implementations fail. Furthermore, we present the extension of SWIG to unprecedentedly large systems, making it a viable implicit solvation method even for molecular mechanics calculations of biological macromolecules.