Linear scaling relationships (LSRs) and Brønsted–Evans–Polanyi (BEP) or transition-state scaling (TSS) relations aid with the prediction of electronic energies. However, temperature effects and pre-exponentials are often taken as constants across metal surfaces or a homologous series. Vibrational scaling relationships (VSRs) offer a way to determine such parameters. Transition-state VSRs (TSVSRs) between local minima and transition states of AH_X (A = C, N, O) surface diffusions correlate with BEP relations and broaden to thermochemical property scaling. Using density functional theory, we extend TSVSRs to AH_X dehydrogenation reactions on transition-metal surfaces, relating vibrational modes of local minima to transition states. We first predict the slopes of the TSS relations by incorporating bond angles using the Slater–Koster structure factors and hybridization through crystal orbital overlap population analysis and energy overlap integrals between adsorbates and metal surfaces. Additionally, we uncover universal thermochemical property scaling, enabling the estimation of entropies and temperature corrections to enthalpies across a homologous series. We demonstrate both significant vibrational corrections in reactions with low intrinsic electronic barriers and considerable variation in the pre-exponential of a simple dehydrogenation reaction across metals and AH_X adsorbates.

中文翻译：

---

预测脱氢的过渡态标度关系和通用过渡态振动和熵相关性

线性标度关系 (LSR) 和 Brønsted-Evans-Polanyi (BEP) 或过渡态标度 (TSS) 关系有助于预测电子能量。然而，温度效应和指数前通常被视为金属表面上的常数或同源系列。振动标度关系 (VSR) 提供了一种确定此类参数的方法。AH _X (A = C, N, O) 表面扩散的局部最小值和过渡态之间的过渡态 VSR (TSVSR)与 BEP 关系相关并扩展到热化学性质缩放。使用密度泛函理论，我们将 TSVSR 扩展到 AH _X过渡金属表面上的脱氢反应，将局部最小值的振动模式与过渡态相关联。我们首先通过结合使用 Slater-Koster 结构因子的键角和通过晶体轨道重叠群分析和吸附物与金属表面之间的能量重叠积分进行杂交来预测 TSS 关系的斜率。此外，我们发现了通用的热化学性质标度，能够估计熵和温度校正到同源序列的焓。我们证明了在具有低固有电子势垒的反应中的显着振动校正以及跨金属和 AH _X吸附物的简单脱氢反应的指数前的显着变化。