Quasiclassical simulations based on cluster models reveal vibration-facilitated roaming in the isomerization of CO adsorbed on NaCl
Quasiclassical simulations based on cluster models reveal vibration-facilitated roaming in the isomerization of CO adsorbed on NaCl
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DOI：
10.1038/s41557-020-00612-y
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发表时间：
2021-01
期刊：
影响因子：
21.8
通讯作者：
Apurba Nandi;Peng Zhang;Jun Chen;Hua Guo;J. Bowman
中科院分区：
文献类型：
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作者：
Apurba Nandi;Peng Zhang;Jun Chen;Hua Guo;J. Bowman
为了更好地理解异构化的量子性质，人们最近对 OC-NaCl(100) 振动诱导异构化为 CO-NaCl(100) 进行了实验观察。为了研究这种异构化的机制，我们使用有限 (CO-NaCl) 团簇模型进行动力学计算。我们使用高级从头计算数据构建了 CO2-NaCl 和 CO2-CO 相互作用的新势能面，并报告了裸 CO2-NaCl 势能面的关键特性，这与实验有很多共同点。我们使用几种簇模型研究了异构化动力学，并且在所有情况下，在高度激发的 CO 振动状态下都观察到异构化，这与实验一致。对反应轨迹的详细检查表明，当 CO 和 NaCl 之间的距离大于传统异构化鞍点的距离时，就会发生异构化，这是“漫游”的强烈指标。
The desire to better understand the quantum nature of isomerization led to recent experimental observations of the vibrationally induced isomerization of OC–NaCl(100) to CO–NaCl(100). To investigate the mechanism of this isomerization, we performed dynamics calculations using finite (CO–NaCl)ncluster models. We constructed new potential energy surfaces for CO–NaCl and CO–CO interactions using high-level ab initio data and report key properties of the bare CO–NaCl potential energy surface, which show much in common with the experiment. We investigated the isomerization dynamics using several cluster models and, in all cases, isomerization was seen for highly excited CO vibrational states, in agreement with experiments. A detailed examination of the reaction trajectories indicates that isomerization occurs when the distance between CO and NaCl is larger than the distance at the conventional isomerization saddle point, which is a strong indicator of ‘roaming’.