Enthalpies of mixing predicted using molecular dynamics simulations and OPLS force field

Dai, Jianxing; Li, Xiaofeng; Zhao, Lifeng; Sun, Huai

doi:10.1016/j.fluid.2009.11.028

Cited by 24 publications

(26 citation statements)

References 40 publications

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“…57 This is a well-established model for methanol and it has been widely used in the literature on simulations of aqueous mixtures. [58][59][60][61][62][63] It reproduces well the thermodynamic experimental behavior of methanol. The OPLS force field also reproduces the solid-solid and solid-fluid equilibria of pure methanol.…”

Section: Simulation Detailssupporting

confidence: 64%

A molecular dynamics study of the equation of state and the structure of supercooled aqueous solutions of methanol

Corradini

Stanley

et al. 2012

The Journal of Chemical Physics

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We perform molecular dynamics computer simulations in order to study the equation of state and the structure of supercooled aqueous solutions of methanol at methanol mole fractions x(m) = 0.05 and x(m) = 0.10. We model the solvent using the TIP4P/2005 potential and the methanol using the OPLS-AA force field. We find that for x(m) = 0.05 the behavior of the equation of state, studied in the P - T and P - ρ planes, is consistent with the presence of a liquid-liquid phase transition, reminiscent of that previously found for x(m) = 0. We estimate the position of the liquid-liquid critical point to be at T = 193 K, P = 96 MPa, and ρ = 1.003 g/cm(3). When the methanol mole fraction is doubled to x(m) = 0.10 no liquid-liquid transition is observed, indicating its possible disappearance at this concentration. We also study the water-water and water-methanol structure in the two solutions. We find that down to low temperature methanol can be incorporated into the water structure for both x(m) = 0.05 and x(m) = 0.10.

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Section: Simulation Detailssupporting

confidence: 64%

A molecular dynamics study of the equation of state and the structure of supercooled aqueous solutions of methanol

Corradini

Stanley

et al. 2012

The Journal of Chemical Physics

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“…We are unsure of the reason for this disagreement; however we must point out that the Δ mix H is a property that is nontrivial to model correctly, and similar deviations from experiment are common in the literature. 97, 99 Through iterative tests on the aromatic carbon’s σ and ε, and through iterative tests on the partial charges of Ben, the Δ mix H changes for Ben + MOH mixtures were always small. Hence, it was not clear which parameters should be modified in order for the model to reach agreement with experiment, and it appeared doubtful that a single Py model could reproduce both the water and methanol data.…”

Section: Resultsmentioning

confidence: 99%

“…Recent investigations seem to indicate that explicit polarization may be required for obtaining accurate enthalpies of mixing, and that even reasonable models can provide incorrect signs. 97,98 The D mix H for Py + MOH indicated that mixing of the solute and solvent was too unfavourable, while the D mix H for Py + water was well reproduced across the full composition range. We are unsure of the reason for this disagreement; however we must point out that the D mix H is a property that is nontrivial to model correctly, and similar deviations from experiment are common in the literature.…”

Section: Solution Propertiesmentioning

confidence: 99%

A Kirkwood–Buff force field for the aromatic amino acids

Ploetz

Smith

2011

Phys. Chem. Chem. Phys.

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In a continuation of our efforts to develop a united atom non-polarizable protein force field based upon the solution theory of Kirkwood and Buff i.e., the Kirkwood-Buff Force Field (KBFF) approach, we present KBFF models for the side chains of phenylalanine, tyrosine, tryptophan, and histidine, including both tautomers of neutral histidine and doubly-protonated histidine. The force fields were specifically designed to reproduce the thermodynamic properties of mixtures over the full composition range in an attempt to provide an improved description of intermolecular interactions. The models were developed by careful parameterization of the solution phase partial charges to reproduce the experimental Kirkwood-Buff integrals for mixtures of solutes representative of the amino acid sidechains in solution. The KBFF parameters and simulated thermodynamic and structural properties are presented for the following eleven binary mixtures: benzene + methanol, benzene + toluene, toluene + methanol, toluene + phenol, toluene + p-cresol, pyrrole + methanol, indole + methanol, pyridine + methanol, pyridine + water, histidine + water, and histidine hydrochloride + water. It is argued that the present approach and models provide a reasonable description of intermolecular interactions which ensures that the required balance between solute-solute, solute-solvent, and solvent-solvent distributions is obtained.

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“…1. Properties of mixtures, especially in the cases of mixtures that deviate strongly from ideality, are sensitive to interactions between functional groups that are not generally present in the pure substances used to train LJ parameters [39,40]. Calculated as in equation 2, simulated enthalpies of mixing directly capture the A-B interactions that enthalpies of vaporization miss.…”

Section: Introductionmentioning

confidence: 99%

Improving force field accuracy by training against condensed phase mixture properties

Boothroyd

Madin

Mobley

et al. 2022

Preprint

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Developing a sufficiently accurate classical force field representation of molecules is key to realizing the full potential of molecular simulation as a route to gaining fundamental insight into a broad spectrum of chemical and biological phenomena. This is only possible, however, if the many complex interactions between molecules of different species in the system are accurately captured by the model. Historically, the intermolecular van der Waals (vdW) interactions have primarily been trained against densities and enthalpies of vaporization of pure (single-component) systems, with occasional usage of hydration free energies. In this study, we demonstrate how including physical property data of binary mixtures can better inform these parameters, encoding more information about the underlying physics of the system in complex chemical mixtures. To demonstrate this, we re-train a select number of the Lennard-Jones parameters describing the vdW interactions of the OpenFF 1.0.0 (Parsley) fixed charge force field against training sets composed of densities and enthalpies of mixing for binary liquid mixtures as well as densities and enthalpies of vaporization of pure liquid systems, and assess the performance of each of these combinations. We show that retraining against the mixture data almost universally improves the force field's ability to reproduce both pure and mixture properties, reducing some systematic errors that exist when training vdW interactions against properties of pure systems only.

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Enthalpies of mixing predicted using molecular dynamics simulations and OPLS force field

Cited by 24 publications

References 40 publications

A molecular dynamics study of the equation of state and the structure of supercooled aqueous solutions of methanol

A molecular dynamics study of the equation of state and the structure of supercooled aqueous solutions of methanol

A Kirkwood–Buff force field for the aromatic amino acids

Improving force field accuracy by training against condensed phase mixture properties

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