Finite-size corrections to the chemical potential
J I Siepmann; I R McDonald; D Frenkel; J I Siepmann; Dept. of Chem., Cambridge Univ., UK; I R McDonald; Dept. of Chem., Cambridge Univ., UK; D Frenkel; Dept. of Chem., Cambridge Univ., UK
Журнал:
Journal of Physics: Condensed Matter
Дата:
1992-01-20
Аннотация:
The particle-insertion method of Widom (1963) has been widely used in numerical simulations for the purpose of calculating the excess chemical potential, mu <sub>ex</sub>. It is known, however, that values of mu <sub>ex</sub> obtained by Widom's method are strongly dependent on N, the number of particles in the system. The authors use the formalism of the grand-canonical ensemble to derive an expression for the leading term in the finite-size correction to mu <sub>ex</sub>. The new expression reduces to the exact result for hard rods and gives numerical results in good agreement with those of simulations of hard-disk and hard-sphere fluids. It is, in both respects, an improvement over an expression previously derived by Smit and Frenkel via a thermodynamic argument.
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