Coarse-grained and reverse-mapped united-atom simulations of long-chain atactic polystyrene melts: Structure, thermodynamic properties, chain conformation, and entanglements

Spyriouni, T; Tzoumanekas, C; Theodorou, D; Muller-Plathe, F; Milano, G

dc.contributor.author	Spyriouni, T	en
dc.contributor.author	Tzoumanekas, C	en
dc.contributor.author	Theodorou, D	en
dc.contributor.author	Muller-Plathe, F	en
dc.contributor.author	Milano, G	en
dc.date.accessioned	2014-03-01T01:26:01Z
dc.date.available	2014-03-01T01:26:01Z
dc.date.issued	2007	en
dc.identifier.issn	0024-9297	en
dc.identifier.uri	https://dspace.lib.ntua.gr/xmlui/handle/123456789/17884
dc.subject	Coarse Grained	en
dc.subject	Thermodynamic Properties	en
dc.subject	Long Chain	en
dc.subject.classification	Polymer Science	en
dc.subject.other	Chemical relaxation	en
dc.subject.other	Computer simulation	en
dc.subject.other	Conformations	en
dc.subject.other	Molecular dynamics	en
dc.subject.other	Monte Carlo methods	en
dc.subject.other	Polystyrenes	en
dc.subject.other	Bonded interactions	en
dc.subject.other	Molecular dynamics simulation	en
dc.subject.other	Nonbonded interactions	en
dc.subject.other	Torsion angles	en
dc.subject.other	Polymer melts	en
dc.title	Coarse-grained and reverse-mapped united-atom simulations of long-chain atactic polystyrene melts: Structure, thermodynamic properties, chain conformation, and entanglements	en
heal.type	journalArticle	en
heal.identifier.primary	10.1021/ma0700983	en
heal.identifier.secondary	http://dx.doi.org/10.1021/ma0700983	en
heal.language	English	en
heal.publicationDate	2007	en
heal.abstract	A coarse-grained model of atactic polystyrene, in which meso and racemo diads are represented as single *superatoms,"" parametrized using Iterative Boltzmann Inversion, has been subjected to connectivity-altering Monte Carlo simulations in order to simulate monodisperse atactic polystyrene melts of molar mass up to 210000 g mol-1 at 500 or 413 K and 1 bar. Analysis of the Monte Carlo results reveals excellent equilibration of chain conformations at all length scales. Chain dimensions, as determined from the mean square end-to-end distance, the mean square radius of gyration, and simulated Kratky plots of the single-chain scattering function, are in excellent agreement with experiment. The equilibrated long-chain configurations are reduced to entanglement networks via topological analysis with the CReTA algorithm. The resulting Kuhn length of primitive paths provides an excellent estimate of the molar mass between entanglements and of the entanglement tube diameter extracted from plateau modulus measurements. The distribution of strand lengths between entanglements, when appropriately reduced, follows the same master curve as previously determined distributions of polyethylene, cis-1,4 polybutadiene, and poly(ethylene terephthalate). A new strategy is introduced for reverse mapping the long-chain coarse-grained configurations into detailed united-atom configurations in a manner that preserves the sequence of diad types along the chains. This strategy employs local ""flip"" Monte Carlo moves to relax the reverse-mapped configurations. Relaxation starts using bonded interactions only, and proceeds by gradually introducing nonbonded interactions. Final relaxation is achieved via short-time canonical molecular dynamics simulation. Predicted wide-angle X-ray diffraction patterns from reverse-mapped configurations are indistinguishable from those of short-chain melts equilibrated directly in the united atom representation using molecular dynamics, and in favorable agreement with experiment. Distributions of torsion angles and pairs of successive torsion angles in the reverse-mapped configurations exhibit some deviations from the corresponding distributions of directly equilibrated short-chain united atom melts and from experimental NMR measurements. © 2007 American Chemical Society.	en
heal.publisher	AMER CHEMICAL SOC	en
heal.journalName	Macromolecules	en
dc.identifier.doi	10.1021/ma0700983	en
dc.identifier.isi	ISI:000246280600052	en
dc.identifier.volume	40	en
dc.identifier.issue	10	en
dc.identifier.spage	3876	en
dc.identifier.epage	3885	en