MOLECULAR SIMULATION STUDIES IN THE SUPERCRITICAL REGION

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MOLECULAR SIMULATION STUDIES IN THE SUPERCRITICAL REGION ( molecular-simulation-studies-insupercritical-region )

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of energy is broader than lower temperatures where is narrower and the advantage has been used at replica exchange methods. Let us assume the case of observing the configurational energy on the critical isochore with temperature, the heat capacity diverges at T=Tc. If you are observing the configurational energy on an isochore, different from the critical isochore i.e. 0.8c the heat capacity becomes maximum at the temperature at which there is phase transition and a large difference is found between the configurational energy of the subcritical and the supercritical phase. We can qualitatively draw the temperature dependence of the internal potential energy across the critical isochore. In the range (0.3-1c) the divergence of the isochoric capacity is quite large and energy which characterises the subcritical region from supercritical one is quite different, so for Monte Carlo is difficult to sample configurations which belong to lower temperatures. However, at lower densities than <0.3c that can happen, Monte Carlo can sample phase configurations with lower characteristic energy and can be trapped there, especially at conditions as the two first points in Figure 7-7. Cv and U Tc T Figure 7-10: Representation of the configurations of the molecules along the critical isotherm. The blue colour indicates a high density region (liquid like) and the red colour a low density region (gas like) Suspecting this situation, we recorded snapshots during Monte Carlo simulation progress. Indeed, the Monte Carlo samples configurations that belong to subcritical phase. In the Figure 7-11, we present a snapshot, which belongs to 107

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