Department of Physics, Purdue University, West Lafayette, Indiana 47907, USA.
J Chem Phys. 2013 May 7;138(17):174908. doi: 10.1063/1.4802258.
A common theoretical approach to calculating reaction kinetics is to approximate a high-dimensional conformational search with a one-dimensional diffusion along an effective reaction coordinate. We employed Brownian dynamics simulations to test the validity of this approximation for loop formation kinetics in the worm-like chain polymer model. This model is often used to describe polymers that exhibit backbone stiffness beyond the monomer length scale. We find that one-dimensional diffusion models overestimate the looping time and do not predict the quantitatively correct dependence of looping time on chain length or capture radius. Our findings highlight the difficulty of describing high-dimensional polymers with simple kinetic theories.
一种常见的计算反应动力学的理论方法是通过沿有效反应坐标的一维扩散来近似高维构象搜索。我们采用布朗动力学模拟来检验这种近似对于蠕虫状链聚合物模型中环化动力学的有效性。该模型常用于描述那些在单体长度尺度之外表现出主链刚性的聚合物。我们发现,一维扩散模型高估了环化时间,并且不能预测环化时间对链长或捕获半径的定量正确的依赖关系。我们的研究结果突出了用简单的动力学理论来描述高维聚合物的困难。