发表机构
Center for Multidimensional Carbon Materials, Institute for Basic Science (IBS); Department of Chemistry, Ulsan National Institute of Science and Technology (UNIST)（多维碳材料中心，韩国基础科学研究所; 蔚山科学技术院化学系）
机构由 AI 辅助整理，请以论文原文为准。AI 中文总结
本文梳理化学速率理论从经验速率常数到机器学习势的演变，阐明不同计算量及其假设，并通过基准测试指导速率比较与活化参数解释。
AI 中文摘要
化学速率理论的重大进展改变了计算的内容以及势垒的含义。我围绕这些变化来组织这一概念史，同时保留理论之间的受控修正和极限关系。计算量包括经验速率常数、碰撞次数、热力学活化自由能、穿过分割面的统计通量、随机逃逸速率、能量分辨的微正则速率、量子通量相关函数，以及使用电子结构或机器学习势计算的反应路径系综。我将假设与先驱作者所陈述的极限进行比较。速率常数是在规定的速率定律下从测量中推断出来的；其温度依赖性定义了表观活化能 $E_a$。活化自由能 $\Delta G^{\ddagger}$、活化焓 $\Delta H^{\ddagger}$、活化熵 $\Delta S^{\ddagger}$、前因子、透射系数 $\kappa$ 和鞍点高度需要动力学模型，并且在相关情况下需要标准态、分割面、系综和动力学修正才能在速率计算中进行解释。在大豆脂氧合酶-1的氢转移中，相似的单同位素活化参数伴随着同位素敏感动力学的巨大变化。五个速率基准测试说明了不同比较所检验的误差，并提出了七项报告项目。这些区分指导了速率的比较和活化参数的解释。
英文摘要
Major advances in chemical rate theory changed what was computed and what a barrier meant. I organize this conceptual history around those changes, while retaining the controlled corrections and limiting relations between theories. The calculated quantities include an empirical rate constant, a collision count, a thermodynamic activation free energy, a statistical flux across a dividing surface, a stochastic escape rate, an energy-resolved microcanonical rate, a quantum flux correlation function, and an ensemble of reactive paths computed with electronic-structure or machine-learned potentials. I compare the assumptions with the limits stated by the pioneering authors. A rate constant is inferred from measurements under a stated rate law; its temperature dependence defines an apparent activation energy $E_a$. Activation free energy $ΔG^{\ddagger}$, activation enthalpy $ΔH^{\ddagger}$, activation entropy $ΔS^{\ddagger}$, the prefactor, transmission coefficient $κ$, and saddle height require a kinetic model and, where relevant, a standard state, dividing surface, ensemble, and dynamical correction for their interpretation in a rate calculation. In hydrogen transfer by soybean lipoxygenase-1, similar single-isotope activation parameters accompany a large change in isotope-sensitive dynamics. Five rate benchmarks illustrate the errors different comparisons test and motivate seven reporting items. These distinctions guide comparisons of rates and interpretations of activation parameters.
CommentsReview article. 41 pages: 31-page main manuscript and 10-page Supplementary Materials; 2 tables and 1 graphical abstract
