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

The potential energysurfaces at the B3LYP-D3-(BJ) level for eightsolutes in dilute aqueous solutions were mapped into simple pairwiseadditive force field expressions using the adaptive force matching(AFM) method. The quality of the fits was validated by computing thehydration free energy (HFE), enthalpy of hydration, and diffusionconstant for each solute. By force matching B3LYP-D3-(BJ), the predictionsfrom the models agree with the closest experimental HFE and enthalpyof hydration within chemical accuracy. The diffusion constants fromthe 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 propertycalculations through AFM for the molecules studied. Accurate computationalpredictions could potentially provide validations to experimentalmeasurements in cases where experimental measurements from differentsources do not agree.

Automated summary

This study mapped potential energy surfaces for eight solutes in dilute aqueous solutions into pairwise additive force field expressions using the AFM method at the B3LYP-D3-(BJ) level. By force matching B3LYP-D3-(BJ), the predictions from the models showed good agreement with experimental data, providing confidence on the quality of producing potential energy surfaces for thermodynamic property calculations. Accurate computational predictions could potentially validate experimental measurements in cases where measurements from different sources do not agree.