Role of torsional potential in chain conformation, thermodynamics, and glass formation of simulated polybutadiene melts

Autor: F. Demydiuk, M. Solar, H. Meyer, O. Benzerara, W. Paul, J. Baschnagel
Přispěvatelé: Institut Charles Sadron (ICS), Université de Strasbourg (UNISTRA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Matériaux et Nanosciences Grand-Est (MNGE), Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS), Martin-Luther-Universität Halle Wittenberg (MLU), Meyer, Hendrik
Rok vydání: 2022
Předmět:
Zdroj: Journal of Chemical Physics
Journal of Chemical Physics, 2022, 156 (23), pp.234902. ⟨10.1063/5.0094536⟩
ISSN: 1089-7690
0021-9606
DOI: 10.1063/5.0094536
Popis: For polymer chains, the torsional potential is an important intramolecular energy influencing chain flexibility and segmental dynamics. Through molecular dynamics simulations of an atomistic model for melts of cis– trans-1,4-polybutadiene (PBD), we explore the effect of the torsions on conformational properties (bond vector correlations and mean-square internal distances), fundamental thermodynamic quantities (density, compressibility, internal energy, and specific heat), and glass transition temperature Tg. This is achieved by systematically reducing the strength of the torsional potential, starting from the chemically realistic chain (CRC) model with the full potential toward the freely rotating chain (FRC) model without the torsional potential. For the equilibrium liquid, we find that the effect of the torsions on polymer conformations is very weak. Still weaker is the influence on the monomer density ρ and isothermal compressibility κ T of the polymer liquid, both of which can be considered as independent of the torsional potential. We show that a van der Waals-like model proposed by Long and Lequeux [Eur. Phys. J. E 4, 371 (2001)] allows us to describe very well the temperature ( T) dependence of ρ and κ T. We also find that our data obey the linear relation between [Formula: see text] and 1/ T (with the Boltzmann constant kB) that has recently been predicted and verified on the experiment by Mirigian and Schweizer [J. Chem. Phys. 140, 194507 (2014)]. For the equilibrium liquid, simulations result in a specific heat, at constant pressure and at constant volume, which increases on cooling. This T dependence is opposite to the one found experimentally for many polymer liquids, including PBD. We suggest that this difference between simulation and experiment may be attributed to quantum effects due to hydrogen atoms and backbone vibrations, which, by construction, are not included in the classical united-atom model employed here. Finally, we also determine Tg from the density–temperature curve monitored in a finite-rate cooling process. While the influence of the torsional potential on ρ( T) is vanishingly small in the equilibrium liquid, the effect of the torsions on Tg is large. We find that Tg decreases by about 150 K when going from the CRC to the FRC model.
Databáze: OpenAIRE
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