title: On the analysis of conformational dynamics in polymers with several rotational isomers.
abstract: The ability of different correlation functions to shed some light onto the conformational dynamics of an amorphous polymer has been analyzed. The study has been performed on a polyethylene model polymer, which has been simulated at decreasing temperatures towards its glass transition, via the molecular dynamics technique. Three rotational isomers are allowed by the considered torsional potential. The correlation times associated with the evaluated transition rates have shown to be Arrhenius in nature, with activation energies resulting basically from internal rotation barriers. Overall torsional autocorrelation functions have been calculated. We have observed that they are dominated by slow events. Alternatively, a set of torsional autocorrelation functions associated with every isomeric state has been evaluated. Stretched exponential fits lead to correlation times that display Vogel-Fulcher temperature dependence.
authors.affiliation: Departament de Física i Enginyeria Nuclear, Universitat Politècnica de Catalunya, Campus Nord-Mòdul B4, c/ Jordi Girona 1-3, 08034 Barcelona, Spain. manel.canales@upc.edu
authors.forename: Manel
authors.initials: M
authors.lastname: Canales
authors.forename: Gemma
authors.initials: G
authors.lastname: Sesé