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The nematic-isotropic phase transition in linear fused hard-sphere chain fluids



We present a modification of the generalized Flory dimer theory to investigate the nematic (N) to isotropic (I) phase transition in chain fluids. We focus on rigid linear fused hard-sphere (LFHS) chain molecules in this study. A generalized density functional theory is developed, which involves an angular weighting of the dimer reference fluid as suggested by decoupling theory, to accommodate nematic ordering in the system. A key ingredient of this theory is the calculation of the exact excluded volume for a pair of molecules in an arbitrary relative orientation, which extends the recent work by Williamson and Jackson for linear tangent hard-sphere chain molecules to the case of linear fused hard-sphere chains with arbitrary intramolecular bondlength. The present results for the N-I transition are compared with previous theories and with computer simulations. In comparison with previous studies, the results show much better agreement with simulations for both the coexistence densities and the nematic order parameter at the transition. (C) 1999 American Institute of Physics. [S0021-9606(99)51023-4].PT: J; CR: BOLHUIS P, 1997, J CHEM PHYS, V106, P666 BOUBLIK T, 1977, CHEM PHYS LETT, V46, P315 BOUBLIK T, 1989, MOL PHYS, V68, P191 CARNAHAN NF, 1969, J CHEM PHYS, V51, P635 CHAMOUX A, 1998, MOL PHYS, V93, P649 CHANDLER D, 1976, J CHEM PHYS, V65, P2925 CHANG J, 1994, CHEM ENG SCI, V49, P2777 CHAPMAN WG, 1988, MOL PHYS, V65, P1057 CHIEW YC, 1990, MOL PHYS, V70, P129 COSTA LA, 1995, J CHEM PHYS, V102, P6212 CURRO JG, 1987, MACROMOLECULES, V20, P1928 FYNEWEVER H, 1998, J CHEM PHYS, V108, P1636 HONNELL KG, 1989, J CHEM PHYS, V90, P1841 JAFFER KM, 1999, THESIS U GUELPH KIERLIK E, 1992, J CHEM PHYS, V97, P9222 KIERLIK E, 1993, J CHEM PHYS, V99, P3950 LEE SD, 1987, J CHEM PHYS, V87, P4972 MEHTA SD, 1996, J PHYS CHEM-US, V100, P10408 ONSAGER L, 1949, ANN NY ACAD SCI, V51, P627 PADILLA P, 1997, J CHEM PHYS, V106, P10299 PARSONS JD, 1979, PHYS REV A, V19, P1225 PRATT LR, 1977, J CHEM PHYS, V66, P147 SCHWEIZER KS, 1988, MACROMOLECULES, V21, P3070 SEN S, 1994, J CHEM PHYS, V101, P9010 SOMOZA AM, 1989, J CHEM PHYS, V91, P517 STELL G, 1964, EQUILIBRIUM THEORY C TILDESLEY DJ, 1980, MOL PHYS, V41, P85 VEGA C, 1994, J CHEM PHYS, V100, P6727 WERTHEIM MS, 1987, J CHEM PHYS, V87, P7323 WHITTLE M, 1991, MOL PHYS, V72, P247 WILLIAMSON DC, 1995, MOL PHYS, V86, P819 WILLIAMSON DC, 1998, J CHEM PHYS, V108, P10294 WOODWARD CE, 1994, J CHEM PHYS, V100, P3181 YETHIRAJ A, 1993, J CHEM PHYS, V98, P1635 YETHIRAJ A, 1995, J CHEM PHYS, V102, P5499 YETHIRAJ A, 1998, MOL PHYS, V93, P693 ZHOU YQ, 1995, J CHEM PHYS, V103, P2688; NR: 37; TC: 15; J9: J CHEM PHYS; PG: 13; GA: 200CHSource type: Electronic(1

Publisher: 'AIP Publishing'
DOI identifier: 10.1063/1.479102
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