Renormalized chemical kinetics and benchmark quantum mechanical rates: activation energies and tunnelling transitivities for the reactions of fluorine atoms with H2 and HD

IF 2.1 4区 综合性期刊 Q2 MULTIDISCIPLINARY SCIENCES Rendiconti Lincei-Scienze Fisiche E Naturali Pub Date : 2023-12-06 DOI:10.1007/s12210-023-01209-6
Valter H. Carvalho-Silva, Flávio O. Sanches-Neto, Guilherme M. Leão, Simonetta Cavalli, Dario De Fazio, Maria C. Nucci, Vincenzo Aquilanti
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Abstract

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.

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重整化化学动力学和基准量子力学速率:氟原子与H2和HD反应的活化能和隧穿传递率
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态或亚稳态结构和近平衡状态的经典分子动力学模拟提供了解释工具和仪器。化学反应动力学在中尺度上起着关键作用:时间依赖和进化问题通常是从现象学上解决的,而通过中间体和过渡态的反应需要研究和建模。在本文中,尺度化和重整化过程超越了Arrhenius方程和过渡态理论,涉及到反应动力学中的两个关键观测值,即速率“常数”作为温度(及其倒数,广义寿命)的函数,以及表观活化能(及其倒数,传递函数)。耦合的一阶方程-依赖于时间和温度-在另一种耦合方案中制定,它们将实验结果与有效的建模联系起来,反之亦然分子动力学模拟与预测。从热隧穿机制的过渡被统一处理,并应用于氟原子与H2和HD的典型三原子反应的速率常数的收敛量子力学计算:这些是由中等隧穿主导的放热过程,需要正式扩展以涵盖低温机制,在低温机制中显示出普遍行为的各个方面。在10-350 K温度范围内的实验信息验证了结果,记录了通常被认为是“基本”化学反应的复杂性:它们与模拟大气和天体物理环境有关。展望了其他类型转变的进展,以及生物物理学和天体化学中应用化学动力学中感兴趣的全球一般过程。
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来源期刊
Rendiconti Lincei-Scienze Fisiche E Naturali
Rendiconti Lincei-Scienze Fisiche E Naturali MULTIDISCIPLINARY SCIENCES-
CiteScore
4.10
自引率
10.00%
发文量
70
审稿时长
>12 weeks
期刊介绍: Rendiconti is the interdisciplinary scientific journal of the Accademia dei Lincei, the Italian National Academy, situated in Rome, which publishes original articles in the fi elds of geosciences, envi ronmental sciences, and biological and biomedi cal sciences. Particular interest is accorded to papers dealing with modern trends in the natural sciences, with interdisciplinary relationships and with the roots and historical development of these disciplines.
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