AI 中文总结
研究探讨艾林图与阿累尼乌斯图，指出艾林表示虽常被认为更具基础性，但谐波近似模型显示阿累尼乌斯图有优势。还阐述了艾林公式中普朗克常数相关问题及维度不匹配，提出替代表示，表明阿累尼乌斯拟合值在物理上更相关。
AI 中文摘要
物理化学文献中的一个普遍观点是，尝试对\(\ln(k/T)\)与\(1/T\)进行线性拟合的艾林表示比\(\ln(k)\)与\(1/T\)的阿累尼乌斯表示更具基础性。这种认知通常源于其从统计力学和量子力学的推导，以及根据活化熵\(\Delta S^\ddagger\)对截距的解释，而阿累尼乌斯方程及其前置因子常被视为纯粹的现象学。然而，谐波近似模型在阿累尼乌斯图中产生精确线性，但在艾林图中并非如此，尽管对于实际实验数据，两者在典型实验精度内通常看起来同样线性。此外，艾林公式本质上是量子力学的印象源于前置因子中普朗克常数的存在，而该术语源于配分函数中的归一化约定。这也突出了基于反应物和过渡态不同维度配分函数的\(\Delta G^\ddagger\)的解释问题。这种维度不匹配可以在一种替代表示中重新表述，该表示提高了可解释性，并简化为一种阿累尼乌斯型表达式，其中前置因子与活化熵直接相关。在此框架下，从阿累尼乌斯拟合得到的活化焓和熵比相应的艾林拟合值在物理上更相关。
英文摘要
A common view in physical chemistry literature is that the Eyring representation, in which a linear fit of $\ln(k/T)$ versus $1/T$ is attempted, is more fundamental than the Arrhenius representation, $\ln(k)$ versus $1/T$. This perception is typically motivated by its derivation from statistical mechanics and quantum mechanics, and by the interpretation of the intercept in terms of the activation entropy $ΔS^\ddagger$, whereas the Arrhenius equation and its prefactor are often regarded as purely phenomenological. However, harmonic approximation models yield exact linearity in Arrhenius plots but not in Eyring plots, although for real experimental data both generally appear equally linear within typical experimental accuracy. Furthermore, the impression that the Eyring formulation is inherently quantum mechanical arises from the presence of the Planck constant in the prefactor, whereas this term results from normalization conventions in the partition function. This also highlights an interpretational issue in $ΔG^\ddagger$, which is based on partition functions of different dimensionality between reactant and transition state. This dimensional mismatch can be reformulated in an alternative representation that improves interpretability and reduces to an Arrhenius-type expression in which the prefactor is directly related to an entropy of activation. In this framework, both activation enthalpy and entropy obtained from an Arrhenius fit are arguably more physically relevant than the corresponding Eyring fit values.
