论文标题

聚合物链生长期间的非平衡自由能

Nonequilibrium free energy during polymer chain growth

论文作者

Bley, Michael, Dzubiella, Joachim

论文摘要

在快速扩散影响的聚合过程中,最近报道了聚合物链和周围反应性单体的非平衡行为。根据热力学定律,某些“额外的自由能”(超过均衡的helmholtz自由能)应该可以表征出现的非平衡结构。在这里,我们研究了自由反应性单体的链生长聚合的非平衡热力学,使用近似反应性的布朗动力学(R-BD)计算机模拟以及近似统计学和相对熵(Gibbs-Shannon和Kullback-blackback-Leibleibler)的概念。在快速生长的聚合物的情况下,我们确实报告说,与平衡和接近平衡的,缓慢生长的链相比,几个KBT的非平衡自由能增加了。有趣的是,额外的自由能是聚合程度的非单调功能,也是时间的非单调功能。我们对热力学贡献的分解表明,最初的显性额外能量存储在自由单体气体的无均衡密度曲线中(显示prossive Centry entive Centry end的无均匀密度谱图(显示密度耗竭和唤醒)。在聚合过程的后期阶段,我们报告了在非平衡聚合物构象中存储的大量额外贡献。最后,我们的研究意味着在聚合后的平衡过程中,非平凡的松弛动力学和额外的自由能的恢复。

During fast diffusion-influenced polymerization, nonequilibrium behavior of the polymer chains and the surrounding reactive monomers has been reported recently. Based on the laws of thermodynamics, the emerging nonequilibrium structures should be characterisable by some "extra free energy" (excess over the equilibrium Helmholtz free energy). Here, we study the nonequilibrium thermodynamics of chain-growth polymerization of ideal chains in a dispersion of free reactive monomers, using off-lattice, reactive Brownian Dynamics (R-BD) computer simulations in conjunction with approximative statistical mechanics and relative entropy (Gibbs-Shannon and Kullback-Leibler) concepts. In case of fast growing polymers, we indeed report increased nonequilibrium free energies of several kBT compared to equilibrium and near-equilibrium, slowly growing chains. Interestingly, the extra free energy is a non-monotonic function of the degree of polymerization and thus also of time. Our decomposition of the thermodynamic contributions shows that the initial dominant extra free energy is stored in the nonequilibrium inhomogeneous density profiles of the free monomer gas (showing density depletion and wakes) in the vicinity of the active center at the propagating polymer end. At later stages of the polymerization process, we report significant extra contributions stored in the nonequilibrium polymer conformations. Finally, our study implies a nontrivial relaxation kinetics and restoring of the extra free energy during the equilibration process after polymerization.

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