Constrained Nuclear-Electronic Orbital Density Functional Theory with a Dielectric Continuum Solvent Model.

Abstract

Solvent effects are crucial for simulating chemical and biological processes in solutions. The continuum solvation model is widely used for incorporating solvent effects with different levels of theoretical descriptions of solutes. For solutes and solutions containing hydrogen atoms, nuclear quantum effects can also be nonnegligible for reliable simulations. In this work, we couple our recently developed constrained nuclear-electronic orbital density functional theory with a dielectric continuum solvation model to cover nuclear quantum effects and solvent effects simultaneously. This approach is applied to the formate ion, where an anomalous solvatochromic shift in C-H stretch frequency was reported in experiments. By using this new approach to account for nuclear quantum effects and solvent effects, we show that the vibrational frequency of the C-H stretch and the solvatochromic shift are accurately described.