TY - JOUR

T1 - Transferable potentials for phase equilibria. 3. Explicit-hydrogen description of normal alkanes

AU - Chen, Bin

AU - Siepmann, J. Ilja

PY - 1999/6/24

Y1 - 1999/6/24

N2 - Motivated by shortcomings of the available united-atom models for alkanes, a new explicit-hydrogen model for n-alkanes (TraPPE-EH, transferable potentials for phase equilibria-explicit hydrogen) is developed from fitting to one-component fluid phase properties. In addition to Lennard-Jones sites on carbon atoms, this model utilizes Lennard-Jones sites on the centers of carbon-hydrogen bonds. Configurational-bias Monte Carlo simulations in the Gibbs and canonical ensembles were carried out to calculate the one-component vapor-liquid phase equilibria for methane to n-dodecane, to determine the phase diagram of supercritical ethane and n-heptane mixtures, to obtain the Gibbs free energies of transfer for n-pentane and n-hexane between helium vapor and n-heptane liquid phases, and to study the high-pressure region of the equation of state for n-pentane and n-decane. The explicit-hydrogen representation with its more faithful description of the molecular shape of alkanes allows us to find a set of Lennard-Jones parameters that yields significantly better agreement with experiment for one- and multicomponent phase equilibria than our united-atom alkane model, but the price is higher computational cost.

AB - Motivated by shortcomings of the available united-atom models for alkanes, a new explicit-hydrogen model for n-alkanes (TraPPE-EH, transferable potentials for phase equilibria-explicit hydrogen) is developed from fitting to one-component fluid phase properties. In addition to Lennard-Jones sites on carbon atoms, this model utilizes Lennard-Jones sites on the centers of carbon-hydrogen bonds. Configurational-bias Monte Carlo simulations in the Gibbs and canonical ensembles were carried out to calculate the one-component vapor-liquid phase equilibria for methane to n-dodecane, to determine the phase diagram of supercritical ethane and n-heptane mixtures, to obtain the Gibbs free energies of transfer for n-pentane and n-hexane between helium vapor and n-heptane liquid phases, and to study the high-pressure region of the equation of state for n-pentane and n-decane. The explicit-hydrogen representation with its more faithful description of the molecular shape of alkanes allows us to find a set of Lennard-Jones parameters that yields significantly better agreement with experiment for one- and multicomponent phase equilibria than our united-atom alkane model, but the price is higher computational cost.

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M3 - Article

AN - SCOPUS:0000378037

VL - 103

SP - 5370

EP - 5379

JO - Journal of Physical Chemistry B Materials

JF - Journal of Physical Chemistry B Materials

SN - 1520-6106

IS - 25

ER -