Free-energy landscape of polymer-crystal polymorphism

• Verfasst von: Liu, Chan [VerfasserIn]
• Verfasst von: Brandenburg, Jan Gerit [VerfasserIn]
• Verfasst von: Valsson, Omar [VerfasserIn]
• Verfasst von: Kremer, Kurt [VerfasserIn]
• Verfasst von: Bereau, Tristan [VerfasserIn]
• Titel: Free-energy landscape of polymer-crystal polymorphism
• Verf.angabe: Chan Liu, Jan Gerit Brandenburg, Omar Valsson, Kurt Kremer, and Tristan Bereau
• E-Jahr: 2020
• Jahr: 03 Sep 2020
• Umfang: 10 S.
• Fussnoten: Gesehen am 24.11.2020
• Titel Quelle: Enthalten in: Soft matter
• Ort Quelle: London : Royal Soc. of Chemistry, 2005
• Jahr Quelle: 2020
• Band/Heft Quelle: 16(2020), 42, Seite 9683-9692
• ISSN Quelle: 1744-6848
• DOI: doi:10.1039/D0SM01342K
• Datenträger: Online-Ressource
• Sprache: eng
• K10plus-PPN: 1740862554

Abstract

Polymorphism rationalizes how processing can control the final structure of a material. The rugged free-energy landscape and exceedingly slow kinetics in the solid state have so far hampered computational investigations. We report for the first time the free-energy landscape of a polymorphic crystalline polymer, syndiotactic polystyrene. Coarse-grained metadynamics simulations allow us to efficiently sample the landscape at large. The free-energy difference between the two main polymorphs, α and β, is further investigated by quantum-chemical calculations. The results of the two methods are in line with experimental observations: they predict β as the more stable polymorph under standard conditions. Critically, the free-energy landscape suggests how the α polymorph may lead to experimentally observed kinetic traps. The combination of multiscale modeling, enhanced sampling, and quantum-chemical calculations offers an appealing strategy to uncover complex free-energy landscapes with polymorphic behavior.