发表机构
Curtin University; University of New South Wales; Adelaide University; Australian National University（科廷大学; 新南威尔士大学; 阿德莱德大学; 澳大利亚国立大学）
机构由 AI 辅助整理，请以论文原文为准。AI 中文总结
本文提出增广Onsager算子与Gateway数，将催化描述符从耗散扩展至非耗散循环，揭示电子自旋调控催化循环，并给出可证伪的磁场调制实验方案。
AI 中文摘要
传统催化描述符评估对称的耗散响应（$\mathcal{D}$），而对与循环催化剂周转相关的反对称、非耗散循环（$\mathcal{L}$）视而不见。我们通过将增广的Onsager算子$\mathcal{A} = \mathcal{D} + \mathcal{L}$应用于催化界面来解决这一问题。通过Onsager-Casimir奇偶规则，我们表明电子自旋在约化状态空间内控制这种非耗散循环，因为反对称耦合需要时间反演奇坐标。我们使用Hasse图映射这些多物理耦合（热-水-力-化学-电-自旋），并引入一个基不变的Gateway数来量化循环相对于耗散的程度，从而将标准的一维火山图扩展为二维活性表面。以掺杂碳上的金属-氮单原子位点作为模型，已发表的电子结构计算提供了静态响应量，由此可以构建两个算子分量。最后，我们提出了一个明确可证伪的实验测试，利用自旋交叉附近的磁场调制来探测量子自旋对该非耗散区域的影响。
英文摘要
Conventional catalytic descriptors evaluate symmetric, dissipative responses ($\mathcal{D}$), remaining blind to the antisymmetric, non-dissipative circulation ($\mathcal{L}$) associated with cyclic catalyst turnover. We address this by applying an augmented Onsager operator, $\mathcal{A} = \mathcal{D} + \mathcal{L}$, to catalytic interfaces. Through Onsager--Casimir parity rules, we show that electron spin governs this non-dissipative circulation within the reduced state space, as antisymmetric coupling necessitates a time-reversal-odd coordinate. We map these multi-physical couplings (Thermo-Hydro-Mechanical-Chemical-Electrical-Spin) using a Hasse diagram and introduce a basis-invariant Gateway number to quantify circulation relative to dissipation, thereby expanding standard one-dimensional volcano plots into a two-dimensional activity surface. Using metal--nitrogen single-atom sites on doped carbon as a model, published electronic-structure calculations supply the static response quantities from which both operator components can be constructed. Finally, we propose an explicitly falsifiable experimental test utilising magnetic field modulation near a spin-crossover to probe the effect of quantum spin on this non-dissipative regime.
CommentsCommunication submitted to JCP, 16 pages 2 figures
