On the Covalent Fields of Molecule-Surface Interactions
关于分子-表面相互作用的共价场
Edvin Fako, Philippe Schwaller
AI总结 提出共价场理论(CFT),将化学亲和性表示为界面连续属性,解决活性位点歧义、BEP关系经验性和线性比例关系不可预测性问题,并在高熵合金和氧化物上验证。
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活性位点的歧义性、Brønsted-Evans-Polanyi关系的经验性以及线性比例关系崩溃的不可预测性,是单一表示选择(将化学亲和性视为离散几何位点的属性)的三个症状。我们在此表明,当化学亲和性被表示为界面的连续属性——共价场时,这三个问题都得到解决。我们提出了一个框架——共价场理论(CFT),其中活性位点作为场维持超过热阈值的成键偏好的区域出现,消除了几何分类的需要。线性比例关系是跨探针家族的场中的相关结构;它们的崩溃是具有精确几何特征的拓扑分岔。Brønsted-Evans-Polanyi相关性源于共价场分解,为先前被视为经验规律的现象提供了理论基础,并在约120,000条候选路径上得到验证。应用于高熵合金纳米颗粒和部分还原的高熵氧化物,CFT将这些性质映射到任意组成和结构复杂性的表面上。
The ambiguity of the active site, the empirical status of Brønsted-Evans-Polanyi relations, and the unpredictability of linear scaling relation breakdown are three symptoms of a single representational choice: treating chemical affinity as an attribute of discrete geometric sites. Here we show that all three are resolved when chemical affinity is represented as a continuous property of the interface: the covalent field. We present a framework, Covalent Field Theory (CFT), in which active sites emerge as regions where the field sustains a bias toward bond formation beyond the thermal threshold, removing the need for geometric classification. Linear scaling relations are correlation structure in the field across probe families; their breakdown is a topological bifurcation with a precise geometric signature. Brønsted-Evans-Polanyi correlations arise from the covalent field decomposition, providing a theoretical basis for what has previously been treated as an empirical regularity, demonstrated across ~120,000 candidate pathways. Applied to a high-entropy alloy nanoparticle and a partially reduced high-entropy oxide, CFT maps these properties onto surfaces of arbitrary compositional and structural complexity.