Predicting hydrophobic solvation by molecular simulation : 1. testing united-atom alkane models

Jorge, Miguel and Garrido, Nuno M. and Simões, Carlos J. V. and Silva, Cândida G. and Brito, Rui M. M. (2017) Predicting hydrophobic solvation by molecular simulation : 1. testing united-atom alkane models. Journal of Computational Chemistry, 38 (6). 346–358. ISSN 0192-8651 (https://doi.org/10.1002/jcc.24690)

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Abstract

We present a systematic test of the performance of three popular united-atom force fields – OPLS-UA, GROMOS and TraPPE – at predicting hydrophobic solvation, more precisely at describing the solvation of alkanes in alkanes. Gibbs free energies of solvation were calculated for 52 solute/solvent pairs from Molecular Dynamics simulations and thermodynamic integration making use of the IBERCIVIS volunteer computing platform. Our results show that all force fields yield good predictions when both solute and solvent are small linear or branched alkanes (up to pentane). However, as the size of the alkanes increases, all models tend to increasingly deviate from experimental data in a systematic fashion. Furthermore, our results confirm that specific interaction parameters for cyclic alkanes in the united-atom representation are required in order to account for the additional excluded volume within the ring. Overall, the TraPPE model performs best for all alkanes, but systematically underpredicts the magnitude of solvation free energies by about 6% (RMSD of 1.2 kJ/mol). Conversely, both GROMOS and OPLS-UA systematically overpredict solvation free energies (by ~13% and 15%, respectively). The systematic trends suggest that all models can be improved by a slight adjustment of their Lennard-Jones parameters.

  • Item type:Article
    ID code:59033
    Dates:
    Date
    Event
    5 March 2017
    Published
    28 December 2016
    Published Online
    18 November 2016
    Accepted
    Notes:This is the peer reviewed version of the following article: Jorge, M. (2016). Predicting hydrophobic solvation by molecular simulation: 1. testing united-atom alkane models. Journal of Computational Chemistry, which has been published in final form at [Link to final article using the DOI]. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving.
    Subjects:Science > Mathematics
    Science > Chemistry
    Department:Faculty of Engineering > Chemical and Process Engineering
    Depositing user: Pure Administrator
    Date deposited:09 Dec 2016 11:15
    Last modified:11 Apr 2024 01:14
    Related URLs:
    URI:https://strathprints.strath.ac.uk/id/eprint/59033
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