التفاصيل البيبلوغرافية
| العنوان: |
The effect of chemical constitution on polyisoprene dynamics. |
| المؤلفون: |
Ghanta, Rohit, Burkhart, Craig, Polińska, Patrycja, Harmandaris, Vagelis, Doxastakis, Manolis |
| المصدر: |
Journal of Chemical Physics; 7/28/2023, Vol. 159 Issue 4, p1-13, 13p |
| مصطلحات موضوعية: |
POLYISOPRENE, INCOHERENT scattering, CONSTITUTIONS |
| مستخلص: |
Polyisoprene (PI) melts have been studied, with most reports focusing on systems with high 1,4-cis content. In contrast, 1,4-trans PI homopolymers or random copolymers have seldom been examined, despite a handful of investigations suggesting a distinct dynamic behavior. Herein, we employ all-atom simulations to investigate the effect of chemical architecture on the dynamics of cis and trans-PI homopolymers, as well as copolymers. We examine the thermodynamic, conformational, and structural properties of the polymers and validate the performance of the models. We probe chain dynamics, revealing that cis-PI presents accelerated translation and reorientation modes relative to trans as recorded by the mean square displacement of the chain center-of-mass as well as by the characteristic times of the lower modes in a Rouse analysis. Interestingly, progressing to higher modes, we observe a reversal with trans units exhibiting faster dynamics. This was further confirmed by calculations of local carbon–hydrogen vector reorientation dynamics, which offer a microscopic view of segmental mobility. To obtain insight into the simulation trajectories, we evaluate the intermediate incoherent scattering function that supports a temperature-dependent crossover in relative mobility that extends over separations beyond the Kuhn-length level. Finally, we analyzed the role of non-Gaussian displacements, which demonstrate that cis-PI exhibits increased heterogeneity in dynamics over short-timescales in contrast to trans-PI, where deviations persist over times extending to terminal dynamics. Our all-atom simulations provide a fundamental understanding of PI dynamics and the impact of microstructure while providing important data for the design and optimization of PI-based materials. [ABSTRACT FROM AUTHOR] |
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| قاعدة البيانات: |
Complementary Index |
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