Monte Carlo study of the coil-to-globule transition of a model polymeric system

Authors

  • Anastassia N. Rissanou,

    1. Institute of Electronic Structure and Laser, Foundation for Research and Technology-Hellas, 711 10 Heraklion Crete, Greece
    2. Department of Physics, University of Crete, 710 03 Heraklion Crete, Greece
    Current affiliation:
    1. Institute of Physical Chemistry, National Center for Scientific Research “Demokritos”, 15310 Aghia Paraskevi Attikis, Greece
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  • Spiros H. Anastasiadis,

    Corresponding author
    1. Institute of Electronic Structure and Laser, Foundation for Research and Technology-Hellas, 711 10 Heraklion Crete, Greece
    2. Department of Physics, University of Crete, 710 03 Heraklion Crete, Greece
    3. Department of Chemical Engineering, Aristotle University of Thessaloniki, 541 24 Thessaloniki, Greece
    • Institute of Electronic Structure and Laser, Foundation for Research and Technology-Hellas, 711 10 Heraklion Crete, Greece
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  • Ioannis A. Bitsanis

    Corresponding author
    1. Institute of Electronic Structure and Laser, Foundation for Research and Technology-Hellas, 711 10 Heraklion Crete, Greece
    • Institute of Electronic Structure and Laser, Foundation for Research and Technology-Hellas, 711 10 Heraklion Crete, Greece
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Abstract

Monte Carlo computer simulations of single, flexible, self-avoiding chains on a cubic lattice have been performed upon conditions of increasing segment–segment cohesive energy (deteriorating solvent quality). The simulations spanned a wide range of chain lengths (20–10,000, i.e., up to molecular weights of a few millions) and cohesive energies (0.0–0.45kBT, i.e., from athermal to very poor solvents). The chain length dependence of the chain size in poor solvents was characterized by a wide plateau of almost null growth for intermediate chain lengths. This plateau was linked to the development of the incipient constant density core, while genuine power law dependence (1/3) was not reached even for the longest chains and poorest solvents simulated here. The mere appearance of a core required substantial chain lengths (higher than 1000; molecular weights of a few hundred thousands), while short chains underwent a gradual densification devoid of any qualitative changes in the density distribution. Sufficiently long chains became more but not quite spherical and underwent a reasonably sharp second order phase transition. The findings were generally in agreement with predictions of mean-field theory and with the use of the standard scaling variables, despite slight inconsistencies. Nevertheless, the results stress the fact that short chains never form a constant density core and that core-dominance on the globule's properties (“volume approximation”) is only valid for extraordinarily long chains [molecular weight of O(109)], an effect linked to the relatively diffuse nature of the surface layer and originating from chain connectivity in conjunction with spherical geometry. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 3651–3666, 2006

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