The calculation of singular points in the supercritical region for a system with a Lennard—Jones interaction potential

详细

In this work the positions of the critical point, the supercritical point, and the maximum fluctuation point in a supercritical isotherm were found for a system with the Lennard—Jones interaction potential. Virial coefficients and methods based on accelerated convergence of the perturbation-theory series, which are well known for such systems, were used. The results were compared with computer-simulation data. As has been established, if one uses the positively defined Weeks—Chandler—Andersen potential as a reference system, the calculated parameters tend monotonically to exact values as a function of the number of virial coefficients. This decomposition is favorably different from the virial one, where the aspiration is not monotonic. These results indicate that this method makes it possible to determine the positions of the three vertices of the supercritical triangle with an accuracy that is comparable to that of a simulated experiment.