Performing Molecular Dynamics Simulations and Computing Hydration Free Energies on the B3LYP-D3(BJ) Potential Energy Surface with Adaptive Force Matching: A Benchmark Study with Seven Alcohols and One Amine.

Abstract

The potential energy surfaces at the B3LYP-D3(BJ) level for eight solutes in dilute aqueous solutions were mapped into simple pairwise additive force field expressions using the adaptive force matching (AFM) method. The quality of the fits was validated by computing the hydration free energy (HFE), enthalpy of hydration, and diffusion constant for each solute. By force matching B3LYP-D3(BJ), the predictions from the models agree with the closest experimental HFE and enthalpy of hydration within chemical accuracy. The diffusion constants from the models are also in good agreement with experimental references. The good agreement provides confidence on the quality of B3LYP-D3(BJ) in producing potential energy surfaces for thermodynamic property calculations through AFM for the molecules studied. Accurate computational predictions could potentially provide validations to experimental measurements in cases where experimental measurements from different sources do not agree.