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our conventional molecular dynamic studies have not revealed any anomaly close to the critical point. 8.6 ISOCHORIC HEAT CAPACITY The constant volume heat capacity, CV can be calculated from the fluctuations in potential energy from MC or MD simulations by O E2E2 CV CV kBT2 (8.7) where E 2 E 2 the potential energy fluctuation, kB is the Boltzmann constant, and T is the absolute temperature. CVO is the ideal gas heat capacity contribution. In case of a polyatomic gas like CO2 the ideal partition function is a product of electronic, nuclear, rotational, translational and vibrational partition functions. According to the procedure being followed in every statistical mechanic text (Van P.Carey, 1999), the formulation gives the ideal part of heat capacity for a polyatomic gas as 3 3 3n6j2 ej/T CV R22 T (ej/T 1)2 (8.8) The first term comes from the translational contribution to the heat capacity, the second term is the rotational contribution and the last term is due to the vibrational degrees of freedom. In the case of carbon dioxide, the rotational contribution is 2/2 since it is a linear molecule. The calculation of ideal heat capacity through statistical mechanics is accurate near the critical temperature, as we can see from Figure 8-12. In Figure 8-13, we present the simulated heat capacity in comparison to the experimental data and values from Wagner’s equation of state. The simulated results are in good agreement, considering the difficulties performing simulations in 127 j1 PDF Image | MOLECULAR SIMULATION STUDIES IN THE SUPERCRITICAL REGION
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