Accurate and local formulation for thermodynamic properties directly from integral equation method |
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Authors: | Shiqi Zhou |
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Institution: | (1) Institute of Modern Statistical Mechanics, Hunan University of Technology, Wenhua Road, Zhuzhou city, 412008, People’s Republic of China |
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Abstract: | A local formulation for determination of excess chemical potential is derived out by applying an assumption of linear dependence
of correlation function and bridge function on the charging parameter to the Kirkwood charging formula and scaling the bridge
function, the scaling parameter is specified by a Gibbs–Duhem relation. The local formulation for the excess chemical potential
only requires the correlation function and bridge function of the investigated state as input and is therefore free of an
unwieldy thermodynamic integration. A comprehensive comparison between the presently calculated thermodynamic quantities for
a Lennard–Jones (LJ) fluid including two key quantities, i.e. the excess chemical potential and excess entropy, corresponding
simulation data available in literature, and corresponding calculated results by several other global and local formulations,
indicates that the present formulation is the only one capable of predicting locally and excellently all of the thermodynamic
properties of the LJ fluid. The GCMC simulation is carried out for a core-softened potential fluid and the LJ fluid near critical
state and at subcritical state near the gas–liquid coexistence line to obtain the excess chemical potential which is also
in excellent agreement with the theoretical prediction from the present formalism; this indicates that the present formalism
is of general interest in fluid statistical mechanics and applicable to parameter space covering over the entire phase diagram. |
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