Fluctuations of conformational mobility of macromolecules around the glass transition

[EN] The heterogeneity of local dynamics in disordered systems is behind some key features of glass transition. In order to improve our understanding of the molecular dynamics in disordered systems in the vicinity of the glass transition, different parameters have been proposed to quantitatively describe dynamical heterogeneity. In the case of polymers, free volume models relate the macromolecular mobility to the free or accessible volume. The relationship between dynamic heterogeneity and fluctuations of accessible volume seems straightforward. In the present work, the heterogeneity of local dynamics in polymeric systems is analyzed by computer simulation with the bond fluctuation model. The value of the accessible volume around each polymer chain is evaluated from a snapshot or static structure at each system state, resulting in a distribution of accessible volume that reflects system heterogeneity. The relationship between the average value and the standard deviation of free volume distributions at different temperatures fits amaster curve for different systems, regardless of the specific inter- and intramolecular interaction potentials that define each material. The dynamic slowdown around the glass transition is accompanied by a clear evolution of the mean value and shape of the accessible free volume distribution. The relative fluctuation of the dynamically accessible volume has been used as a parameter to quantitatively describe heterogeneity. The fluctuation varies with temperature with remarkable differences between the liquid and glassy states of the systems studied, presenting a peak at the glass transition temperature, which can be interpreted as a reflection of the distribution of local glass transition temperatures.The support from the Ministry of Economy and Competitiveness (Spain) through Project No. MAT2016-76039-C4-1-R (including the FEDER financial support) is gratefully acknowledged. R.S.S. acknowledges the support of the Ministry of Education, Culture and Sports (Spain) through the program "Estancias de movilidad de profesores e investigadores seniores en centros extranjeros de ensenanza superior e investigacion 2016 under Grant No. PRX16/00208". CIBER-BBN is an initiative funded by the VI National R&D&I Plan 2008-2011, Iniciativa Ingenio 2010, Consolider Program. CIBER Actions are financed by the Instituto de Salud Carlos III with assistance from the European Regional Development Fund.Torregrosa Cabanilles, C.; Molina Mateo, J.; Sabater I Serra, R.; Meseguer Dueñas, JM.; Gómez Ribelles, JL. (2018). Fluctuations of conformational mobility of macromolecules around the glass transition. Physical Review E. 97(6):062605-1-062605-7. https://doi.org/10.1103/PhysRevE.97.062605062605-1062605-797