Polarisation corrections and the hydration free energy of water

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Abstract

Classical non-polarisable water models play a crucial role in computer simulations due to their simplicity and computational efficiency. However, the neglect of explicit polarisation can jeopardise their accuracy and predictive capabilities, particularly for properties that involve a change in electrostatic environment (e.g. phase changes). In order to mitigate this intrinsic shortcoming, highly simplified analytical polarisation corrections describing the distortion of the molecular dipole are commonly applied in force field development and validation. In this paper, we perform molecular dynamics simulations and thermodynamic integration to show that applying the current state-of-the-art polarisation corrections leads to a systematic inability of current non-polarisable water models to simultaneously predict the experimental enthalpy of vaporisation and hydration free energy. We go on to extend existing theories of polarisation and combine them with data from recent ab initio molecular dynamics simulations to obtain a better estimate of the real contribution of polarisation to phase-change energies and free energies. Our results show that for strongly polar molecules like water, the overall polarisation correction is close to zero, resulting from a cancellation of multipole distortion and purely electronic polarisation effects. In light of these findings, we suggest that parametrisation of classical non-polarisable models of water should be revisited in an attempt to simultaneously describe phase-change energetics and other thermodynamic and structural properties of the liquid.
Original languageEnglish
Number of pages14
JournalJournal of Chemical Theory and Computation
Early online date16 Dec 2018
DOIs
Publication statusE-pub ahead of print - 16 Dec 2018

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Hydration
Free energy
hydration
free energy
Polarization
Water
polarization
water
Molecular dynamics
Computer simulation
molecular dynamics
Computational efficiency
Vaporization
cancellation
multipoles
field theory (physics)
Structural properties
Electrostatics
Enthalpy
Thermodynamic properties

Keywords

  • computer simulations
  • polarisation corrections
  • molecular dynamics simulations
  • water models

Cite this

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title = "Polarisation corrections and the hydration free energy of water",
abstract = "Classical non-polarisable water models play a crucial role in computer simulations due to their simplicity and computational efficiency. However, the neglect of explicit polarisation can jeopardise their accuracy and predictive capabilities, particularly for properties that involve a change in electrostatic environment (e.g. phase changes). In order to mitigate this intrinsic shortcoming, highly simplified analytical polarisation corrections describing the distortion of the molecular dipole are commonly applied in force field development and validation. In this paper, we perform molecular dynamics simulations and thermodynamic integration to show that applying the current state-of-the-art polarisation corrections leads to a systematic inability of current non-polarisable water models to simultaneously predict the experimental enthalpy of vaporisation and hydration free energy. We go on to extend existing theories of polarisation and combine them with data from recent ab initio molecular dynamics simulations to obtain a better estimate of the real contribution of polarisation to phase-change energies and free energies. Our results show that for strongly polar molecules like water, the overall polarisation correction is close to zero, resulting from a cancellation of multipole distortion and purely electronic polarisation effects. In light of these findings, we suggest that parametrisation of classical non-polarisable models of water should be revisited in an attempt to simultaneously describe phase-change energetics and other thermodynamic and structural properties of the liquid.",
keywords = "computer simulations, polarisation corrections, molecular dynamics simulations, water models",
author = "Milne, {Andrew W.} and Miguel Jorge",
year = "2018",
month = "12",
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doi = "10.1021/acs.jctc.8b01115",
language = "English",
journal = "Journal of Chemical Theory and Computation",
issn = "1549-9618",
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AU - Jorge, Miguel

PY - 2018/12/16

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N2 - Classical non-polarisable water models play a crucial role in computer simulations due to their simplicity and computational efficiency. However, the neglect of explicit polarisation can jeopardise their accuracy and predictive capabilities, particularly for properties that involve a change in electrostatic environment (e.g. phase changes). In order to mitigate this intrinsic shortcoming, highly simplified analytical polarisation corrections describing the distortion of the molecular dipole are commonly applied in force field development and validation. In this paper, we perform molecular dynamics simulations and thermodynamic integration to show that applying the current state-of-the-art polarisation corrections leads to a systematic inability of current non-polarisable water models to simultaneously predict the experimental enthalpy of vaporisation and hydration free energy. We go on to extend existing theories of polarisation and combine them with data from recent ab initio molecular dynamics simulations to obtain a better estimate of the real contribution of polarisation to phase-change energies and free energies. Our results show that for strongly polar molecules like water, the overall polarisation correction is close to zero, resulting from a cancellation of multipole distortion and purely electronic polarisation effects. In light of these findings, we suggest that parametrisation of classical non-polarisable models of water should be revisited in an attempt to simultaneously describe phase-change energetics and other thermodynamic and structural properties of the liquid.

AB - Classical non-polarisable water models play a crucial role in computer simulations due to their simplicity and computational efficiency. However, the neglect of explicit polarisation can jeopardise their accuracy and predictive capabilities, particularly for properties that involve a change in electrostatic environment (e.g. phase changes). In order to mitigate this intrinsic shortcoming, highly simplified analytical polarisation corrections describing the distortion of the molecular dipole are commonly applied in force field development and validation. In this paper, we perform molecular dynamics simulations and thermodynamic integration to show that applying the current state-of-the-art polarisation corrections leads to a systematic inability of current non-polarisable water models to simultaneously predict the experimental enthalpy of vaporisation and hydration free energy. We go on to extend existing theories of polarisation and combine them with data from recent ab initio molecular dynamics simulations to obtain a better estimate of the real contribution of polarisation to phase-change energies and free energies. Our results show that for strongly polar molecules like water, the overall polarisation correction is close to zero, resulting from a cancellation of multipole distortion and purely electronic polarisation effects. In light of these findings, we suggest that parametrisation of classical non-polarisable models of water should be revisited in an attempt to simultaneously describe phase-change energetics and other thermodynamic and structural properties of the liquid.

KW - computer simulations

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KW - molecular dynamics simulations

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