Computational Aspects of Single-Molecule Kinetics for Coupled Catalytic Cycles: A Spectral Analysis
Computational Aspects of Single-Molecule Kinetics for Coupled Catalytic Cycles: A Spectral Analysis
复制标题
耦合催化循环的单分子动力学的计算方面：光谱分析
DOI：
10.1021/acs.jpca.2c02153
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发表时间：
2022
期刊：
影响因子：
--
通讯作者：
Skodje, Rex T.
中科院分区：
文献类型：
--
作者：
An, Suming;Patel, Prajay;Liu, Cong;Skodje, Rex T.
使用从单分子动力学开发的方法分析来自单个活性位点的催化。使用随机马尔可夫状态描述，一般催化反应网络的可观察的属性表示使用马尔可夫过程的转移矩阵的特征值分解。通过灵敏度分析，所需的本征值和本征向量与位于反应路线沿着的控制势垒和威尔斯的能量有关。一个概括的充满活力的跨度理论允许的本征值计算从几个激活能对应于不同的势垒-阱配对。形式主义证明模型问题和一个物理上现实的烯烃加氢反应的单原子催化剂上的机制。光谱分析允许从单分子信号识别时间尺度的层次结构，其对应于网络中的特定弛豫模式。
Catalysis from single active sites is analyzed using methods developed from single-molecule kinetics. Using a stochastic Markov-state description, the observable properties of general catalytic networks of reactions are expressed using an eigenvalue decomposition of the transition matrix for the Markov process. By the use of a sensitivity analysis, the necessary eigenvalues and eigenvectors are related to the energies of controlling barriers and wells located along the reaction routes. A generalization of the energetic span theory allows the eigenvalues to be computed from several activation energies corresponding to distinct barrier-well pairings. The formalism is demonstrated for model problems and for a physically realistic mechanism for an alkene hydrogenation reaction on a single-atom catalyst. The spectral analysis permits a hierarchy of timescales to be identified from the single-molecule signal, which correspond to specific relaxation modes in the network.