Issue 42, 2020

Free-energy landscape of polymer-crystal polymorphism

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.

Graphical abstract: Free-energy landscape of polymer-crystal polymorphism

Supplementary files

Article information

Article type
Paper
Submitted
23 Jūl. 2020
Accepted
02 Sept. 2020
First published
03 Sept. 2020
This article is Open Access
Creative Commons BY license

Soft Matter, 2020,16, 9683-9692

Free-energy landscape of polymer-crystal polymorphism

C. Liu, J. G. Brandenburg, O. Valsson, K. Kremer and T. Bereau, Soft Matter, 2020, 16, 9683 DOI: 10.1039/D0SM01342K

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

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