Abstract
A continuum mean field approach based on Generalized Flory Theory and the Polymer Reference Interaction Site Model is developed to describe the structural and equation of state properties of normal alkane liquids and linear polyethylene melts. Efficient Monte Carlo simulations based on a new algorithm that employs concerted rotations around up to seven consecutive skeletal bonds along a chain are also conducted on the same systems. A realistic united-atom model is chosen to describe the geometry and energetics of the molecules and used throughout the study. Comparisons between the simulations and experimental thermodynamic and structural results are good and those between the mean field theory and the exact simulation results are reasonable. A method is described for quickly sampling the conformation of unperturbed chains in continuous space. The statistics of these chains compare very well with conformationally equilibrated chain statistics from the bulk simulation; this provides a confirmation of Flory's Random Coil Hypothesis. The need for improving the mean field theory and for enhancing the equilibration rate of the Monte Carlo simulations are identified. A new neighbor-list scheme is introduced for use in polymer Monte Carlo simulations.
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6 References
Dickman R, Hall C (1986) J Chem Phys 85: 4108
Honnell K, Hall CK (1989) J Chem Phys 90: 1841
Flory PJ (1953) Principles of polymer chemistry. Cornell University Press, Ithaca
Schweizer KS, Curro JG (1987) Phys Rev Lett 58: 246
Curro JG, Schweizer KS (1987) Macromolecules 20: 1928
Honnell KG, McCoy JD, Curro JG, Schweizer KS, Narten AH, Habenschuss A (1991) J Chem Phys 94: 4659
Chandler D (1982) In: Montroll E, Lebowitz J (eds) The liquid state of matter: Fluids, simple and complex, North Holland, p 275 (Studies in Statistical Mechanics, vol VIII)
Yethiraj A, Hall C (1991) J Chem Phys 95: 1999
Yethiraj A, Hall C (1991) J Chem Phys 95: 8494
Curro JG, Schweizer KS, Grest GS, Kremer K (1989) J Chem Phys 91: 1357
Allen M, Tildesley D (1987) Computer Simulation of Liquids, Oxford Science Publications, Oxford
Rigby D, Roe R-J (1987) J Chem Phys 87: 7285
Rigby D, Roe R-J (1988) J Chem Phys 89: 5280
Rigby D, Roe R-J (1989) Macromolecules 22: 2259
Brown D, Clarke JHR (1991) Comput Phys Commun 62: 360
Brown D, Clarke JHR (1991) Macromolecules 24: 2075
Takeuchi H, Roe R-J (1991) J Chem Phys 94: 7446
Takeuchi H, Roe R-J (1991) J Chem Phys 94: 7458
Boyd RH, Pant PVK (1991) Macromolecules 24: 6325
Pant PVK, Han J, Smith GD, Boyd RH (1993) J Chem Phys 99: 597
Yoon DY, Smith GD, Matsuda T (1993) J Chem Phys 98: 10037
Smith GD, Yoon DY (1993) J Chem Phys, submitted
Vacatello M, Avitabile G, Corradini P, Tuzi A (1980) J Chem Phys 73: 548
Boyd RH (1989) Macromolecules 22: 2477
de Pablo JJ, Laso M, Suter UW (1992) J Chem Phys 96: 2395
Siepmann JI, Frenkel D (1992) Molec Phys 75: 59
Dodd LR, Boone TD, Theodorou DN (1993) Molec Phys 78: 961
Leontidis EM, de Pablo JJ, Laso M, Suter UW (1993) Submitted to Advan Polym Sci
Gō N, Scheraga HA (1976) Macromolecules 9: 535
Theodorou DN, Boone TD, Dodd LR, Mansfield KF (1992) Makromol Chem, Theory Simul 2: 191
de Pablo JJ (1992) Personal Communication
Ryckaert JP, Bellemans A (1975) Chem Phys Lett 30: 123
Theodorou DN, Suter UW (1985) Macromolecules 18: 1467
Mansfield KF, Theodorou DN (1990) Macromolecules 23: 4430
Dodd LR, Theodorou DN (1992) Polym Prepr (Am Chem Soc, Div Polym Chem) 33: 645
Flory PJ (1969) Statistical mechanics of chain molecules. Wiley, New York
Ciccotti G, Ryckaert J (1986) Comput Phys Rep 4: 345, Appendix A by H.J.C. Berendsen
Dee G, Ougizawa T, Walsh D (1992) Polymer 33: 3462
Gillan M (1979) Molec Phys 38: 1781
Habenschuss A, Narten A (1990) J Chem Phys 92: 5692
Ertl H, Dullien F (1973) AIChE J 19: 1215
Barker J, Henderson D (1967) J Chem Phys 47: 4714
Yethiraj A, Curro JG, Schweizer KS, McCoy JD (1993) J Chem Phys 98: 1635
Curro JG, Yethiraj A, Schweizer KS, McCoy JD, Honnell KG (1993) Macromolecules 26: 2655
Dodd LR, Theodorou DN (1991) Molec Phys 72: 1313
Grest GS, Dünweg B, Kremer K (1989) Comput Phys Commun 55: 269
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© 1994 Springer-Verlag
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Dodd, L.R., Theodorou, D.N. (1994). Atomistic Monte Carlo simulation and continuum mean field theory of the structure and equation of state properties of alkane and polymer melts. In: Monnerie, L., Suter, U.W. (eds) Atomistic Modeling of Physical Properties. Advances in Polymer Science, vol 116. Springer, Berlin, Heidelberg . https://doi.org/10.1007/BFb0080201
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DOI: https://doi.org/10.1007/BFb0080201
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