AI 中文总结
该研究提出Lewis标记图（LLG）模型，将弯箭头等电子流符号转化为可执行规则，经实验验证其能准确重放反应并拒绝篡改，为反应机理建模提供通用可执行状态空间。
AI 中文摘要
弯箭头形式体系是有机反应机理的通用语言，但它无法被执行。基于规则的建模中使用的分子图编码原子连接性，却省略了孤对电子、自由基电子以及不同的σ和π组分。因此拓扑匹配无法确定反应中心是否持有某一步骤消耗的电子，而基于衍生形式电荷的匹配会拒绝那些确实持有该电子的中心。我们引入Lewis标记图（Lewis-labeled graph, LLG），其原子标记包含孤对电子和自由基布居，键标记则区分σ和π键的占据数。键级、形式电荷和价电子总量可由这些字段推导得出。化学转化成为资源受限的双推出规则，弯箭头和耦合鱼钩符号则成为从共同预状态原子提交的位点排序电子转移。对于指定的事件组，我们证明其执行、应用其诱导的规则以及相应的积分占据更新是等价的。每个可允许的事件都守恒价电子和净形式电荷，且以键为中心的鱼钩耦合源于积分性而非绘图惯例。双向重放恢复了全部39,732个映射参考终点，同时LLG比传统原子-键规则少产生96个正向唯一结果和818个逆向唯一结果。10条自由基记录需要手动注释修正。经审核，101,314条记录中有101,313条成功构建过渡态，剩余案例需修正终点原子映射而非箭头编辑。严格重放接受全部160条已审核步骤，并拒绝全部1,120条受控篡改。这些结果为分子图、反应规则和电子流注释建立了一个通用可执行状态空间，适用于动力学或热力学可行性问题之前的研究。
英文摘要
The curly-arrow formalism is the lingua franca of organic reaction mechanisms, but it is not executable. Molecular graphs used in rule-based modeling encode atomic connectivity while omitting lone pairs, radical electrons, and distinct sigma and pi components. Topological matching therefore cannot determine whether a reactive center holds the electrons a step consumes, while matching on derived formal charge can reject centers that do hold them. We introduce the Lewis-labeled graph (LLG), whose atom labels carry lone-pair and radical populations and whose bond labels separate sigma- and pi-bond occupancies. Bond order, formal charge, and valence electron inventory are derived from these fields. Chemical transformations become resource-constrained double-pushout rules, and curly arrows and coupled fishhooks become locus-sorted electron transfers committed atomically from a common pre-state. For a specified event group, we prove that its execution, application of its induced rule, and the corresponding integral occupancy update are equivalent. Every admissible event conserves valence electrons and net formal charge, and bond-centered fishhook coupling follows from integrality rather than drawing convention. Bidirectional replay recovers all 39,732 mapped reference endpoints, while LLG admits 96 fewer forward and 818 fewer inverse unique outcomes than conventional atom-bond rules. Ten radical records require manual annotation corrections. After review, transition construction succeeds for 101,313 of 101,314 records. The remaining case requires an endpoint atom-map correction rather than an arrow edit. Strict replay accepts all 160 reviewed steps and rejects all 1,120 controlled corruptions. These results establish a common executable state space for molecular graphs, reaction rules, and electron-flow annotations, prior to questions of kinetic or thermodynamic feasibility.
Comments32 pages, 12 figures, 5 tables, including Supporting Information
