AI 中文总结
该研究针对共价机械化学缺乏预测凝聚态物质反应动力学理论框架的问题，开发非微扰理论框架，可捕获高应变分子活化能垒变化，实现多尺度预测，通过一般可观测量表达式，用简单计算预测机械化学效应，以螺吡喃为例进行了验证。
AI 中文摘要
共价机械化学领域已从基础科学过渡到工程应用，但缺乏预测凝聚态物质中反应动力学的强大理论框架。现有分析模型在宏观应变驱动高度非线性分子尺度变形的现实条件下失效。我们开发了一个非微扰理论框架，该框架捕获了经历复杂非线性变形的高应变分子中的活化能垒变化，描述了宏观-纳米尺度现象的耦合。该框架产生可从原子模拟参数化的一般表达式，能够对机械化学行为进行多尺度预测。通过以一般可观测量给出这些表达式，这项工作能够从简单的结构优化计算预测机械化学效应，从而能够使用高级量子化学方法。我们在机械变色聚合物螺吡喃上展示了这种方法，展示了非线性应变场如何控制机械发色团的活化。
英文摘要
The field of covalent mechanochemistry has transitioned from fundamental science to engineering applications, yet it lacks a robust theoretical framework for predicting reaction kinetics in condensed matter. Existing analytical models fail under realistic conditions where macroscopic strains drive molecular-scale deformations that are highly non-linear. We develop a non-perturbative theoretical framework that captures activation barrier changes in highly strained molecules undergoing complex, non-linear deformations, describing the macroscale-nanoscale coupling of phenomena. The framework yields general expressions, parameterizable from atomistic simulations, enabling multiscale prediction of mechanochemical behavior. By presenting the expressions in terms of general observables, this work enables predictions of mechanochemical effects from simple structure optimization calculations, enabling the use of high level quantum chemical methods. We demonstrate this approach on the mechanochromic polymer spiropyran, showing how non-linear strain fields govern mechanophore activation.
