Rapid Atom-Based Analysis of the Intramolecular Dynamics of Polymers

本研究的目的是一个定量的，计算效率高的，基于原子的大分子旋转异构动力学描述。这种形式可以用来确定进入链的任何特定构象子集的初始通道的速率。理论形式主义的有效性将通过两种类型的实验来评估。第一种实验是在实验室用真正的分子进行的，是测量产生分子内准分子的构象子集的占据动力学，作为发色团的荧光寿命、化学结构和柔性片段的长度的函数，柔性片段的构象属于产生准分子发射的子集。第二个实验是用计算机进行的，是一个计算密集的分子动力学模拟，用飞秒时间步长，其结果将与从计算上更有效的动态旋转异构态理论得到的结果进行比较。

The objective of this research is a quantitative, computationally efficient, atom-based description of the dynamics of rotational isomerism in macromolecules. The formalism can be used to determine the rate of initial passage into any specified subset of the conformations of the chain. The validity of the theoretical formalism will be assessed by two types of experiments. The first type of experiment, performed in the laboratory with real molecules, is the measurement of the dynamics of the occupation of that subset of conformations that produces an intramolecular excimer, to be performed as functions of the fluorescence lifetime of the chromophore, chemical structure and length of the flexible fragment, and conformations of the flexible fragment that belong to the subset that produces excimer emission. The second experiment, performed with a computer, is a computationally intensive molecular dynamics simulation, with femptosecond time steps, the results of which will be compared with those obtained from the computationally much more efficient dynamic rotational isomeric state theory.