MOLECULAR DYNAMIC SIMULATION AND EQUATION OF STATE OF LENNARD-JONES CHAIN FLUIDS

Chang J; Kim H

Korean Journal of Chemical Engineering, Vol.15, No.5, 544-551, September, 1998

In order to study the thermodynamic properties of chain and polymeric fluids at the molecular level, we perform constant temperature molecular dynamics simulations of 'repulsive' and 'full' Lennard-Jones (LJ) chain fluids of lengths up to 16. In the simulation, the RATTLE algorithm to determine constraint forces and the Nose-Hoover thermostat to sample the canonical ensemble are used. For repulsive LJ chains, the compressibility factor of the chain fluids is predicted from first-order thermodynamic perturbation theory combined with the Week-Chandler-An-dersen (TPT1-WCA) perturbation theory, and is compared to the simulation results. A good agreement between the theory and the simulation results is found particularly at liquid-like densities. For full LJ chains, two different versions of TPT1 are used to calculate the compressibility factor : one is TPT1-WCA, and the other is TPT1 with the Percus-Yevick approximation for the radial distribution function of the LJ spheres (TPT1-PY). At low and intermediate densities, TPT1-PY gives better predictions for the compressibility of the LJ chain fluids, whereas at high densities TPT1-WCA is more reliable.

Keywords:Equation of State;Molecular Dynamics;Thermodynamic Perturbation Theory;Lennard-Jones;Chain Fluid

[References]

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[Referenced By]

[1] Allen MP, Tildesley DJ, "Computer Simulation of Liquids," Clarendon Press, Oxford (1987)

[2] Andersen HC, J. Comput. Phys., 52, 24 (1983)

[3] Banaszak M, Chiew YC, Olenick R, Radosz M, J. Chem. Phys., 100(5), 3803 (1994)

[4] Chang J, Sandler SI, Chem. Eng. Sci., 49(17), 2777 (1994)

[5] Chapman WG, Jackson G, Gubbins KE, Mol. Phys., 65, 1057 (1988)

[6] Chapman WG, Gubbins KE, Jackson G, Radosz M, Ind. Eng. Chem. Res., 29, 1709 (1990)

[7] Gao J, Weiner JH, J. Chem. Phys., 91, 3168 (1989)

[8] Ghonasgi D, Chapman WG, J. Chem. Phys., 100(9), 6633 (1994)

[9] Honnell KG, Hall CK, J. Chem. Phys., 90, 1841 (1989)

[10] Hoover WG, Phys. Rev., A, 31, 1695 (1985)

[11] Huang SH, Radosz M, Ind. Eng. Chem. Res., 29, 2284 (1990)

[12] Johnson JK, Muller EA, Gubbins KE, J. Phys. Chem., 98(25), 6413 (1994)

[13] Lee LL, "Molecular Thermodynamics of Nonideal Fluids," Butterworths (1988)

[14] Li XJ, Chiew YC, Chem. Eng. Sci., 49(17), 2805 (1994)

[15] Li XJ, Chiew YC, J. Chem. Phys., 101(3), 2522 (1994)

[16] Nicolas JJ, Gubbins KE, Streett WB, Tildesley DJ, Mol. Phys., 37, 1429 (1979)

[17] Nose S, Mol. Phys., 52, 255 (1984)

[18] Panagiotopoulos AZ, Mol. Phys., 61, 813 (1987)

[19] Ryckaert JP, Ciccotti G, Berendsen HJC, J. Comput. Phys., 23, 327 (1977)

[20] Tavares FW, Chang J, Sandler SI, Mol. Phys., 86, 1451 (1995)

[21] Verlet L, Weis JJ, Phys. Rev., A, 5, 939 (1972)

[22] Weeks JD, Chandler D, Andersen HC, J. Chem. Phys., 54, 5237 (1971)

[23] Wertheim MS, J. Stat. Phys., 35, 19 (1984)

[24] Wertheim MS, J. Stat. Phys., 35, 35 (1984)

[25] Wertheim MS, J. Stat. Phys., 42, 459 (1986)

[26] Wertheim MS, J. Stat. Phys., 42, 477 (1986)

[27] Wertheim MS, J. Chem. Phys., 87, 7323 (1987)