Experimental, theoretical and computational chemical kinetics contribute to progress both in molecular and materials sciences and in biochemistry, exploring the gap between elementary processes and complex systems. Stationary state quantum mechanics and statistical thermodynamics provide interpretive tools and instruments for classical molecular dynamics simulations for stable or metastable structures and near-equilibrium situations. Chemical reaction kinetics plays a key role at the mesoscales: time-dependent and evolution problems are typically tackled phenomenologically, and reactions through intermediates and transition states need be investigated and modelled. In this paper, scaling and renormalization procedures are developed beyond the Arrhenius equation and the Transition State Theory, regarding two key observables in reaction kinetics, the rate “constant” as a function of temperature (and its reciprocal, the generalised lifetime), and the apparent activation energy (and its reciprocal, the transitivity function). Coupled first-order equations—dependent on time and on temperature—are formulated in alternative coupling scheme they link experimental results to effective modelling, or vice versa molecular dynamics simulations to predictions. The passage from thermal to tunnelling regimes is uniformly treated and applied to converged quantum mechanical calculations of rate constants available for the prototypical three-atom reactions of fluorine atoms with both H₂ and HD: these are exothermic processes dominated by moderate tunnel, needing formal extension to cover the low-temperature regime where aspects of universal behaviour are shown to emerge. The results that have been validated towards experimental information in the 10–350 K temperature range, document the complexity of commonly considered “elementary” chemical reactions: they are relevant for modelling atmospheric and astrophysical environments. Perspectives are indicated of advances towards other types of transitions and to a global generality of processes of interest in applied chemical kinetics in biophysics and in astrochemistry.

实验、理论和计算化学动力学有助于分子和材料科学以及生物化学的进步，探索基本过程和复杂系统之间的差距。稳态量子力学和统计热力学为稳定或亚稳态结构和近平衡情况的经典分子动力学模拟提供了解释工具和仪器。化学反应动力学在介观尺度上起着关键作用：时间依赖性和演化问题通常通过现象学来解决，并且需要研究和建模通过中间体和过渡态的反应。在本文中，缩放和重整化程序超越了阿伦尼乌斯方程和过渡态理论，涉及反应动力学中的两个关键可观察量，即作为温度函数的速率“常数”（及其倒数，广义寿命），以及表观活化能（及其倒数，传递函数）。耦合一阶方程（取决于时间和温度）以替代耦合方案表示，它们将实验结果与有效建模联系起来，反之亦然，分子动力学模拟与预测联系起来。从热态到隧道态的过渡经过统一处理，并应用于氟原子与 H ₂和 HD 的典型三原子反应可用的速率常数的聚合量子力学计算：这些是由中度隧道主导的放热过程，需要形式扩展涵盖低温状况，其中显示出普遍行为的各个方面。已针对 10-350 K 温度范围内的实验信息进行验证的结果记录了通常认为的“基本”化学反应的复杂性：它们与大气和天体物理环境建模相关。展望了其他类型的转变以及生物物理学和天体化学中应用化学动力学感兴趣的全球普遍性过程的进展。