A polarization-consistent model for alcohols to predict solvation free energies

Research output: Contribution to journalArticle

Abstract

Classical non-polarizable models, normally based on a combination of Lennard-Jones sites and point charges, are extensively used to model thermodynamic properties of fluids, including solvation. An important shortcoming of these models is that they do not explicitly account for polarization effects - i.e. a description of how the electron density responds to changes in the molecular environment. Instead, polarization is implicitly included, in a mean-field sense, into the parameters of the model, usually by fitting to pure liquid properties (e.g. density). This causes problems when trying to describe thermodynamic properties that involve a change of phase (e.g. enthalpy of vaporization), that directly depend on the electronic response of the medium (e.g. dielectric constant), and that require mixing or solvation in different media (e.g. solvation free energies). Fully polarisable models present a natural route for addressing these limitations, but at the price of a much higher computational cost. In this work, we combine the best of those two approaches, by running fast simulations using non-polarizable models and applying post facto corrections to the computed properties in order to account for the effects of polarization. By applying this new paradigm, a new united-atom force field for alcohols is developed that is able to predict both pure liquid properties, including dielectric constant, and solvation free energies in different solvents with a high degree of accuracy. This paves the way for the development of a generic classical non-polarizable force field that can predict solvation of drug-like molecules in a variety of solvents.
Original languageEnglish
Number of pages16
JournalJournal of Chemical Information and Modeling
Early online date24 Jan 2020
DOIs
Publication statusE-pub ahead of print - 24 Jan 2020

Fingerprint

Solvation
polarization
Free energy
Alcohols
alcohol
Polarization
energy
Permittivity
Thermodynamic properties
Liquids
Vaporization
Carrier concentration
Enthalpy
electronics
paradigm
drug
Atoms
simulation
Molecules
Fluids

Keywords

  • thermodynamic properties
  • fluids
  • polarization effects

Cite this

@article{ba01264b8ca746ef89b5813a069d2924,
title = "A polarization-consistent model for alcohols to predict solvation free energies",
abstract = "Classical non-polarizable models, normally based on a combination of Lennard-Jones sites and point charges, are extensively used to model thermodynamic properties of fluids, including solvation. An important shortcoming of these models is that they do not explicitly account for polarization effects - i.e. a description of how the electron density responds to changes in the molecular environment. Instead, polarization is implicitly included, in a mean-field sense, into the parameters of the model, usually by fitting to pure liquid properties (e.g. density). This causes problems when trying to describe thermodynamic properties that involve a change of phase (e.g. enthalpy of vaporization), that directly depend on the electronic response of the medium (e.g. dielectric constant), and that require mixing or solvation in different media (e.g. solvation free energies). Fully polarisable models present a natural route for addressing these limitations, but at the price of a much higher computational cost. In this work, we combine the best of those two approaches, by running fast simulations using non-polarizable models and applying post facto corrections to the computed properties in order to account for the effects of polarization. By applying this new paradigm, a new united-atom force field for alcohols is developed that is able to predict both pure liquid properties, including dielectric constant, and solvation free energies in different solvents with a high degree of accuracy. This paves the way for the development of a generic classical non-polarizable force field that can predict solvation of drug-like molecules in a variety of solvents.",
keywords = "thermodynamic properties, fluids, polarization effects",
author = "Barrera, {Maria Cecilia} and Miguel Jorge",
year = "2020",
month = "1",
day = "24",
doi = "10.1021/acs.jcim.9b01005",
language = "English",
journal = "Journal of Chemical Information and Modeling",
issn = "1549-9596",
publisher = "American Chemical Society",

}

TY - JOUR

T1 - A polarization-consistent model for alcohols to predict solvation free energies

AU - Barrera, Maria Cecilia

AU - Jorge, Miguel

PY - 2020/1/24

Y1 - 2020/1/24

N2 - Classical non-polarizable models, normally based on a combination of Lennard-Jones sites and point charges, are extensively used to model thermodynamic properties of fluids, including solvation. An important shortcoming of these models is that they do not explicitly account for polarization effects - i.e. a description of how the electron density responds to changes in the molecular environment. Instead, polarization is implicitly included, in a mean-field sense, into the parameters of the model, usually by fitting to pure liquid properties (e.g. density). This causes problems when trying to describe thermodynamic properties that involve a change of phase (e.g. enthalpy of vaporization), that directly depend on the electronic response of the medium (e.g. dielectric constant), and that require mixing or solvation in different media (e.g. solvation free energies). Fully polarisable models present a natural route for addressing these limitations, but at the price of a much higher computational cost. In this work, we combine the best of those two approaches, by running fast simulations using non-polarizable models and applying post facto corrections to the computed properties in order to account for the effects of polarization. By applying this new paradigm, a new united-atom force field for alcohols is developed that is able to predict both pure liquid properties, including dielectric constant, and solvation free energies in different solvents with a high degree of accuracy. This paves the way for the development of a generic classical non-polarizable force field that can predict solvation of drug-like molecules in a variety of solvents.

AB - Classical non-polarizable models, normally based on a combination of Lennard-Jones sites and point charges, are extensively used to model thermodynamic properties of fluids, including solvation. An important shortcoming of these models is that they do not explicitly account for polarization effects - i.e. a description of how the electron density responds to changes in the molecular environment. Instead, polarization is implicitly included, in a mean-field sense, into the parameters of the model, usually by fitting to pure liquid properties (e.g. density). This causes problems when trying to describe thermodynamic properties that involve a change of phase (e.g. enthalpy of vaporization), that directly depend on the electronic response of the medium (e.g. dielectric constant), and that require mixing or solvation in different media (e.g. solvation free energies). Fully polarisable models present a natural route for addressing these limitations, but at the price of a much higher computational cost. In this work, we combine the best of those two approaches, by running fast simulations using non-polarizable models and applying post facto corrections to the computed properties in order to account for the effects of polarization. By applying this new paradigm, a new united-atom force field for alcohols is developed that is able to predict both pure liquid properties, including dielectric constant, and solvation free energies in different solvents with a high degree of accuracy. This paves the way for the development of a generic classical non-polarizable force field that can predict solvation of drug-like molecules in a variety of solvents.

KW - thermodynamic properties

KW - fluids

KW - polarization effects

U2 - 10.1021/acs.jcim.9b01005

DO - 10.1021/acs.jcim.9b01005

M3 - Article

JO - Journal of Chemical Information and Modeling

JF - Journal of Chemical Information and Modeling

SN - 1549-9596

ER -