Henry’s Law Constant from Molecular Simulation: A Systematic Study of 95 Systems

Huang, Yow-Lin; Miroshnichenko, Svetlana; Hasse, Hans; Vrabec, Jadran

doi:10.1007/s10765-009-0684-1

Cited by 17 publications

(17 citation statements)

References 69 publications

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“…While other approaches have been used to calculate solvation free energies, alchemical free energy calculations using explicit solvent have become a mainstream approach, , in part because of their formal rigor. Alternative approaches include implicit-solvent models, − , which yield Δ G hyd but do not take into consideration the solvent configuration around the solute, and Monte Carlo-based approaches using the Gibbs ensemble − and expanded ensemble, though these are most commonly used for molecules that are particularly small and/or rigid.…”

Section: Introductionmentioning

confidence: 99%

Approaches for Calculating Solvation Free Energies and Enthalpies Demonstrated with an Update of the FreeSolv Database

et al. 2017

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Solvation free energies can now be calculated precisely from molecular simulations, providing a valuable test of the energy functions underlying these simulations. Here, we briefly review “alchemical” approaches for calculating the solvation free energies of small, neutral organic molecules from molecular simulations, and illustrate by applying them to calculate aqueous solvation free energies (hydration free energies). These approaches use a non-physical pathway to compute free energy differences from a simulation or set of simulations and appear to be a particularly robust and general-purpose approach for this task. We also present an update (version 0.5) to our FreeSolv database of experimental and calculated hydration free energies of neutral compounds and provide input files in formats for several simulation packages. This revision to FreeSolv provides calculated values generated with a single protocol and software version, rather than the heterogeneous protocols used in the prior version of the database. We also further update the database to provide calculated enthalpies and entropies of hydration and some experimental enthalpies and entropies, as well as electrostatic and nonpolar components of solvation free energies.

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Section: Introductionmentioning

confidence: 99%

Approaches for Calculating Solvation Free Energies and Enthalpies Demonstrated with an Update of the FreeSolv Database

et al. 2017

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“…The force fields for Ar, N 2 , and O 2 were taken from the work of Vrabec et al These force fields were adjusted to experimental VLE data and it was shown that they are an adequate choice for numerous fluid mixtures. ,− For H 2 O, the widely appreciated TIP4P/2005 force field, which performs well for a large variety of thermodynamic properties, − was employed.…”

Section: Methodsmentioning

confidence: 99%

Molecular Models for the Hydrogen Age: Hydrogen, Nitrogen, Oxygen, Argon, and Water

2018

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Thermodynamic properties including the phase behavior of all mixtures containing hydrogen, the main air components nitrogen, oxygen, and argon, as well as water are of particular interest for the upcoming postcarbon age. Molecular modeling and simulation, the PC-SAFT equation of state, and sophisticated empirical equations of state are employed to study the mixture behavior of these five substances. For this purpose, a new force field for hydrogen is developed. All relevant subsystems, that is, binary, ternary, and quaternary mixtures, are considered. The quality of the results is assessed by comparing to available experimental literature data, showing an excellent agreement in many cases. Molecular simulation, which is the most versatile approach in general, also provides the best overall agreement. Consequently, this contribution aims at an improved availability of thermodynamic data that are required for the hydrogen age.

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“…Although the Lorentz-Berthelot combining rules are widely used to model binary mixtures, there is room for improvement. So, we have followed the procedure of Huang et al (2009) which consists in introducing an adjustable parameter, , in the Lorentz-Berthelot rule for the pair energy parameter, ,…”

Section: Appendixmentioning

confidence: 99%

Vesicularity, bubble formation and noble gas fractionation during MORB degassing

2013

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42 pages, 8 figures. To be published in Chemical GeologyInternational audienceThe objective of this study is to use molecular dynamics simulation (MD) to evaluate the vesicularity and noble gas fractionation, and to shed light on bubble formation during MORB degassing. A previous simulation study (Guillot and Sator (2011) GCA 75, 1829-1857) has shown that the solubility of CO2 in basaltic melts increases steadily with the pressure and deviates significantly from Henry's law at high pressures (e.g. 9.5 wt% CO2 at 50 kbar as compared with 2.5 wt% from Henry's law). From the CO2 solubility curve and the equations of state of the two coexisting phases (silicate melt and supercritical CO2), deduced from the MD simulation, we have evaluated the evolution of the vesicularity of a MORB melt at depth as function of its initial CO2 contents. An excellent agreement is obtained between calculations and data on MORB samples collected at oceanic ridges. Moreover, by implementing the test particle method (Guillot and Sator (2012) GCA 80, 51-69), the solubility of noble gases in the two coexisting phases (supercritical CO2 and CO2-saturated melt), the partitioning and the fractionation of noble gases between melt and vesicles have been evaluated as function of the pressure. We show that the melt/CO2 partition coefficients of noble gases increase significantly with the pressure whereas the large distribution of the 4He/40Ar* ratio reported in the literature is explained if the magma experiences a suite of vesiculation and vesicle loss during ascent. By applying a pressure drop to a volatile bearing melt, the MD simulation reveals the main steps of bubble formation and noble gas transfer at the nanometric scale. A key result is that the transfer of noble gases is found to be driven by CO2 bubble nucleation, a finding which suggests that the diffusivity difference between He and Ar in the degassing melt has virtually no effect on the 4He/40Ar* ratio measured in the vesicles

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Henry’s Law Constant from Molecular Simulation: A Systematic Study of 95 Systems

Cited by 17 publications

References 69 publications

Approaches for Calculating Solvation Free Energies and Enthalpies Demonstrated with an Update of the FreeSolv Database

Approaches for Calculating Solvation Free Energies and Enthalpies Demonstrated with an Update of the FreeSolv Database

Molecular Models for the Hydrogen Age: Hydrogen, Nitrogen, Oxygen, Argon, and Water

Vesicularity, bubble formation and noble gas fractionation during MORB degassing

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