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away from the central one, we haveN N(t) N , in which case the isothermal compressibility can be written as N(t) N T N As T reaches its maximum near the critical point, it undergoes large fluctuations about its average value over time. As MD trajectories through solving the Newton equation in order to find the positions of molecules with time, they have a difficulty following the fast movement of the molecules in “real” carbon dioxide, so they underestimate the value of isothermal compressibility. It also has to be considered that these density fluctuations near the critical point are correlated over a long range (radial distribution function decays slowly) so that larger systems are required to describe properly the molecules that are entering a fixed volume and the molecules that are exiting it at a given distance for r in g(r). As fluctuation in local structure is high, possibly more time consuming simulations required to improve the accuracy of the calculated isothermal compressibilities near critical density. It is not so difficult to imagine that this kind of inhomogeneity effects the kinetic energy distribution. Sometimes it can cause a serious breakdown even in the constant-temperature molecular dynamics simulation by Berendsen method.However, even with these improvements it will be a discrepancy between real and of the predicted value because of the nature of molecular dynamics and the nature the microscopic structure of the real world of fluids. This fact does not reduce the incredible value of the molecular dynamics simulations, as they mimic the physical movements of the molecules in the compressible regime at a satisfactory level resulting in quite reliable predictions. 122PDF Image | MOLECULAR SIMULATION STUDIES IN THE SUPERCRITICAL REGION
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