Intramolecular Reaction Rates of Flexible Polymers. 1. Simulation Results and the Classical Theory
Intramolecular Reaction Rates of Flexible Polymers. 1. Simulation Results and the Classical Theory
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DOI：
10.1021/ma980254t
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发表时间：
1998-10
期刊：
影响因子：
5.5
通讯作者：
Marta Ortiz-Repiso;J. J. Freire-J.;Antonio Rey
中科院分区：
文献类型：
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作者：
Marta Ortiz-Repiso;J. J. Freire-J.;Antonio Rey
我们用布朗动力学数值算法模拟了在稀溶液中柔性聚合物链中发生的可逆分子内反应。模拟是基于高斯链模型，包括远程相互作用的可能性，以模拟排除体积条件。流体动力学的相互作用被认为是在不同层次的细节。我们已经扩展了我们以前的研究，端到端的环化更长的链，并增加了环化过程中涉及内部单元的分析。环化速率常数的数值计算结果与经典的Wilemski和Fixman环化理论的结果进行了系统的比较，以更好地理解理论近似的效果。前面描述的短链的结论一般得到证实，虽然在某些情况下，他们变得稍微修正了这项工作的更准确的结果。此外，我们还将分析扩展到端到内部和走廊到内部。
We have used a Brownian dynamics numerical algorithm to simulate reversible intramolecular reactions taking place in flexible polymer chains in dilute solutions. The simulations are based on the Gaussian chain model, with the possibility of including long range interactions to mimic excluded volume conditions. Hydrodynamic interactions are considered at different levels of detail. We have extended our previous study of end-to-end cyclizations to longer chains and added the analysis of cyclization processes involving inner units. The numerical results of the cyclization rate constants are systematically compared with the results of the classical cyclization theory of Wilemski and Fixman, to better understand the effect of the theoretical approximations. The conclusions previously described for shorter chains are confirmed in general, though in some cases they become slightly corrected by the more accurate results of this work. In addition, we have extended our analysis to end-to-interior and interior-to-in...