Predicting hydrophobic solvation by molecular simulation : 2. new united-atom model for alkanes, alkenes and alkynes

Jorge, Miguel (2017) Predicting hydrophobic solvation by molecular simulation : 2. new united-atom model for alkanes, alkenes and alkynes. Journal of Computational Chemistry, 38 (6). 359–369. ISSN 0192-8651 (https://doi.org/10.1002/jcc.24689)

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Abstract

Existing united-atom models for non-polar hydrocarbons lead to systematic deviations in predicted solvation free energies in hydrophobic solvents. In this paper, an improved set of parameters is proposed for alkane molecules that corrects this systematic deviation and accurately predicts solvation free energies in hydrophobic media, while simultaneously providing a very good description of pure liquid densities. The model is then extended to alkenes and alkynes, again yielding very accurate predictions of solvation free energies and densities for these classes of compounds. For alkynes in particular, this work represents the first attempt at a systematic parameterization using the united-atom approach. Averaging over all 95 solute/solvent pairs tested, the mean signed deviation from experimental data is very close to zero, indicating no systematic error in the predictions. The fact that predictions are robust even for relatively large molecules suggests that the new model may be applicable to solvation of non-polar macromolecules without accumulation of errors. The root mean squared deviation of the simulations is only 0.6 kJ/mol, which is lower than the estimated uncertainty in the experimental measurements. This excellent performance constitutes a solid basis upon which a more general model can be parameterized to describe solvation in both polar and non-polar environments.

ORCID iDs

Jorge, Miguel ORCID logoORCID: https://orcid.org/0000-0003-3009-4725;
  • Item type:Article
    ID code:59034
    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: 2. new united-atom model for alkanes, alkenes and alkynes. 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:18 Nov 2024 19:11
    Related URLs:
    URI:https://strathprints.strath.ac.uk/id/eprint/59034
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