The segmental (bond) rotational dynamics in a polymer melt of unentangled, linear bead-spring chains is studied by molecular dynamics simulations. To single out the connectivity effects, states with limited deviations from the Gaussian behavior of the linear displacement are considered. Both the self and the cross bond-bond correlations with rank l=1,2 are studied in detail. For l=1 the correlation functions are precisely described by expressions involving the correlation functions of the chain modes. Several approximations concerning both the self- and the cross-correlations with l=1,2 are developed and assessed. It is found that the simplified description of the excluded volume static effects derived elsewhere [D. Molin , J. Phys.: Condens. Matter 18, 7543 (2006)] well accounts for the short time cross-correlations. It also allows a proper modification of the Rouse theory which provides quantitative account of the intermediate and the long time decay of the rotational correlations with l=1.
|Autori:||Ottochian A; Molin D; Barbieri A; Leporini D|
|Titolo:||Connectivity effects in the segmental self- and cross-reorientation of unentangled polymer melts|
|Anno del prodotto:||2009|
|Digital Object Identifier (DOI):||10.1063/1.3262307|
|Appare nelle tipologie:||1.1 Articolo in rivista|