PW-SMD: A Plane-Wave Implicit Solvation Model Based on Electron Density for Surface Chemistry and Crystalline Systems in Aqueous Solution

作者：Yang Wang, Chong Teng, Elijah Begin, Mason Bussiere, Junwei Lucas Bao · 发表于：Journal of Chemical Theory and Computation · 年份：2024 · DOI：10.1021/acs.jctc.4c00594 · 被引用次数：21 · 研究领域：Spectroscopy and Quantum Chemical Studies、Photochemistry and Electron Transfer Studies、Advanced Chemical Physics Studies

Electron density-based implicit solvation models are a class of techniques for quantifying solvation effects and calculating free energies of solvation without an explicit representation of solvent molecules. Integral to the accuracy of solvation modeling is the proper definition of the solvation shell separating the solute molecule from the solvent environment, allowing for a physical partitioning of the free energies of solvation. Unlike state-of-the-art implicit solvation models for molecular quantum chemistry calculations, e . g ., the solvation model based on solute electron density (SMD), solvation models for systems under periodic boundary conditions with plane-wave (PW) basis sets have been limited in their accuracy. Furthermore, a unified implicit solvation model with both homogeneous solution-phase and heterogeneous interfacial structures treated on equal footing is needed. In order to address this challenge, we developed a high-accuracy solvation model for periodic PW calculations that is applicable to molecular, ionic, interfacial, and bulk-phase chemistry. Our model, PW-SMD, is an extension of the SMD molecular solvation model to periodic systems in water. The free energy of solvation is partitioned into the electrostatic and cavity–dispersion–solvent structure (CDS) contributions. The electrostatic contributions of the solvation shell surrounding solute structures are parametrized based on their geometric and physical properties. In addition, the nonelectrostati...