Development and Application of Hybrid AIMD/cDFT Simulations for Atomic-to-Mesoscale Chemistry

Many important geochemical and biogeochemical processes involve reactivity and dynamics in complex solutions. Gaining a fundamental understanding of these reaction mechanisms is a challenging goal that requires advanced computational and experimental approaches. However, important techniques such as molecular simulation have limitations in terms of scales of time, length and system complexity. Furthermore, among currently available solvation models, there are very few designed to describe the interaction between the molecular scale and mesoscale. To help address this challenge, here we establish a novel hybrid approach that couples first principle plane-wave density functional theory (DFT) with classical density functional theory (cDFT). In this approach, a region of interest described by ab initio molecular dynamics (AIMD) interacts with the surrounding medium described using cDFT to arrive at a self-consistent ground state. cDFT is a robust but efficient mesoscopic approach to accurate thermodynamics of bulk electrolyte solutions over a wide concentration range (up to 2 molar concentrations). Benchmarking against commonly used continuum models of solvation such as SMD, as well as experiment, demonstrates that our hybrid AIMD/cDFT method is able to produce reasonable solvation energies for a variety of molecules and ions. With this model, we also examined solvent effects on a prototype S$_N$2 reaction of the nucleophilic attack of a chloride ion on methyl chloride in solution. The resulting reaction pathway profile and the solution phase barrier agree well with the experiment, showing that our AIMD/cDFT hybrid approach can provide insight into the specific role of solvent on the reaction coordinate.