Visualization of electron density changes along chemical reaction pathways
Visualization of electron density changes along chemical reaction pathways
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DOI：
10.1080/00268976.2022.2113566
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发表时间：
2022-08
影响因子：
1.7
通讯作者：
Chance Lander;Vardhan Satalkar;Junjie Yang;Xiaoliang Pan;Zheng Pei;Aayushi Chatterji;Chungen Liu;K. Nicholas;R. Cichewicz;Zhibo Yang;Y. Shao
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文献类型：
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作者：
Chance Lander;Vardhan Satalkar;Junjie Yang;Xiaoliang Pan;Zheng Pei;Aayushi Chatterji;Chungen Liu;K. Nicholas;R. Cichewicz;Zhibo Yang;Y. Shao
我们提出了一个简单的程序可视化的电子密度变化（EDC）在化学反应过程中，这是基于一个固定的结构到（扭曲）的位置周围的原子的另一个固定的结构的矩形网格点的映射。具体地，在沿着最小能量路径（MEP）的小步骤沿着期间，每个网格点的位移被获得为所有原子的运动的线性组合，其中来自每个原子的贡献由相应的Hirshfeld权重缩放。对于几个反应（身份S $ _N $N2，Claisen重排，Diels-Alder反应，$ [3 +2] $ [3+2]环加成，和苯乙基醚攻击周苷A），我们的EDC图显示了预期的减少周围的电子密度切断键（或那些与键级降低），与观察到的相反，新形成或增强的化学键。EDC图也显示了三氟甲磺酸铜催化的N2 O断裂，其中N-O键弱化最初发生在单线态表面上，但在达到两个势能面之间的最小能量交叉点（MECP）后在三线态表面上继续。图形摘要
We propose a simple procedure for visualising the electron density changes (EDC) during a chemical reaction, which is based on a mapping of rectangular grid points for a stationary structure into (distorted) positions around atoms of another stationary structure. Specifically, during a small step along the minimum energy pathway (MEP), the displacement of each grid point is obtained as a linear combination of the motion of all atoms, with the contribution from each atom scaled by the corresponding Hirshfeld weight. For several reactions (identity S $ _N $ N2, Claisen rearrangement, Diels-Alder reaction, $ [3+2] $ [3+2] cycloaddition, and phenylethyl mercaptan attack on pericosine A), our EDC plots showed an expected reduction of electron densities around severed bonds (or those with the bond-order lowered), with the opposite observed for newly-formed or enhanced chemical bonds. The EDC plots were also shown for copper triflate catalyzed N $ _2 $ 2O fragmentation, where the N–O bond weakening initially occurred on a singlet surface, but continued on a triplet surface after reaching the minimum-energy crossing point (MECP) between the two potential energy surfaces. GRAPHICAL ABSTRACT