A systematic approach to calibrate a transferable polarizable force field parameter set for primary alcohols

Abstract

In this work, parameters are optimized for a charge-on-spring based polarizable force field for linear alcohols. We show that parameter transferability can be obtained using a systematic approach in which the effects of parameter changes on physico-chemical properties calculated from simulation are predicted. Our previously described QM/MM calculations are used to attribute condensed-phase polarizabilities, and starting from the non-polarizable GROMOS 53A5/53A6 parameter set, van der Waals and Coulomb interaction parameters are optimized to reproduce pure-liquid (thermodynamic, dielectric, and transport) properties, as well as hydration free energies. For a large set of models, which were obtained by combining small perturbations of 10 distinct parameters, values for pure-liquid properties of the series methanol to butanol were close to experiment. From this large set of models, we selected 34 models without special repulsive van der Waals parameters to distinguish between hydrogen-bonding and non-hydrogen-bonding atom pairs, to make the force field simple and transparent. © 2017 Wiley Periodicals, Inc.

Molecular Dynamics Simulations of Ionic Liquids and Electrolytes Using Polarizable Force Fields

“…Beyond water, additional pure solvents or neat liquids have played a central role in development of the additive CHARMM force field and the Drude polarizable model, not to mention their central role as target data for development of OPLS, 307 AMBER, 307 GROMOS, 308 APPLE&P, 44,309 and other force fields. 310 The advantage of pure solvents is the availability of accurate experimental data on properties including the density (or molecular volume), the heat of vaporization, the isothermal compressibility, and the dielectric permittivity, among others. This offers data that allows for, in particular, Lennard-Jones parameters to be systematically optimized, especially in the context of a hierarchical optimization approach.…”

Insights into Noncovalent Binding Obtained from Molecular Dynamics Simulations

“…While such an assignment would be difficult to perform manually it has to be ensured that automatically assigned parameters are consistent with the macromolecular force field applied to the other components of the system such that a combination of quantum chemical calculations with some heuristic rules will most likely deliver the most appropriate results. This will remain an on‐going challenge for force field development as the complexity and heterogeneity of systems studied by molecular simulation increases .…”

Deriving Force-Field Parameters from First Principles Using a Polarizable and Higher Order Dispersion Model

“…15−19 We recently showed that the additional electrostatic parameters in nonadditive force fields (polarizabilities of the inducible dipole moments) can be derived from combined QM/MM calculations in the condensed phase, and we successfully applied this approach in first parametrization studies. 20−22…”

“…For that purpose bonded parameters describing bond stretching and angle bending have been directly and successfully derived in several automated parametrization protocols , from quantum mechanical (QM) Hessian calculations. Electrostatic parameters can be derived from a gas-phase ground-state calculation, either by fitting the molecular electrostatic potential on a grid around the compound resulting in electrostatic potential (ESP) derived charges − or by partitioning the computed electron density in an atoms-in-molecules (AIM) manner, where the difference between the effective number of electrons and the nuclear charge determines the partial charge of the atoms. − We recently showed that the additional electrostatic parameters in nonadditive force fields (polarizabilities of the inducible dipole moments) can be derived from combined QM/MM calculations in the condensed phase, and we successfully applied this approach in first parametrization studies. − …”