Quantum Tunneling in Reactions Modulated by External Electric Fields: Reactivity and Selectivity.
Quantum Tunneling in Reactions Modulated by External Electric Fields: Reactivity and Selectivity.
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DOI：
10.1021/acs.jpclett.2c03461
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发表时间：
2023-01
期刊：
影响因子：
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通讯作者：
Zhifeng Ma;Zeyin Yan;Xin Li;L. Chung
中科院分区：
文献类型：
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作者：
Zhifeng Ma;Zeyin Yan;Xin Li;L. Chung
量子隧穿和外电场（EEFs）可以促进某些反应。然而，EEF的协同效应的隧道涉及的反应和它的温度依赖性是不是很清楚。在这项研究中，我们广泛研究了EEFs如何影响三个反应，涉及氢或（基态和激发态）碳隧穿使用可靠的DFT，DLPNO-CCSD（T1），变分过渡态理论方法。我们的研究表明，取向EEFs可以显着降低势垒和相应的势垒宽度（反之亦然），通过更多的静电稳定过渡态。这些EEF效应提高了非隧穿和隧穿参与率。这种EEF效应也降低了交叉温度和量子隧穿贡献，尽管具有更低和更薄的势垒。此外，EEFs可以调制和开关隧道驱动的羟基卡宾在低温条件下的1，2-H迁移。此外，我们的研究首次预测，EEF/隧道协同作用可以控制一个具有两个相似/相同反应位点的分子的化学或位点选择性。
Quantum tunneling and external electric fields (EEFs) can promote some reactions. However, the synergetic effect of an EEF on a tunneling-involving reaction and its temperature-dependence is not very clear. In this study, we extensively investigated how EEFs affect three reactions that involve hydrogen- or (ground- and excited-state) carbon-tunneling using reliable DFT, DLPNO-CCSD(T1), and variational transition-state theory methods. Our study revealed that oriented EEFs can significantly reduce the barrier and corresponding barrier width (and vice versa) through more electrostatic stabilization in transition states. These EEF effects enhance the nontunneling and tunneling-involving rates. Such EEF effects also decrease the crossover temperatures and quantum tunneling contribution, albeit with lower and thinner barriers. Moreover, EEFs can modulate and switch on/off the tunneling-driven 1,2-H migration of hydroxycarbenes under cryogenic conditions. Furthermore, our study predicts for the first time that EEF/tunneling synergy can control the chemo- or site-selectivity of one molecule bearing two similar/same reactive sites.