Control of nuclear dynamics in the benzene cation by electronic wavepacket composition.
Control of nuclear dynamics in the benzene cation by electronic wavepacket composition.
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DOI：
10.1038/s42004-021-00485-3
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发表时间：
2021-04-01
影响因子：
5.9
通讯作者：
Robb, Michael A.
中科院分区：
文献类型：
--
作者：
Tran, Thierry;Worth, Graham A.;Robb, Michael A.
由电子态相干叠加驱动的耦合电子-核动力学的研究现在可以在阿秒科学实验中实现。目的是了解化学反应的电子控制。在这项工作中，我们报告了苯自由基阳离子的相干 8 态非绝热电子核动力学模拟。计算受到极紫外 (XUV) 实验结果的启发，其中所有 8 个电子态均以大量布居准备。我们的目标是使用各种定制的相干电子态叠加作为量子埃伦菲斯特方法的初始条件来研究核动力学。最初的 XUV 测量得到多配置时间相关 Hartree (MCTDH) 模拟的支持，该模拟提出了连续通过圆锥形交叉点的模型。目前的计算支持一个补充模型，其中非绝热事件在远离圆锥形交叉点的地方可见，并由涉及非相邻绝热态的电子动力学控制。事实证明，可以识别与两个可能的碎片路径相关联的两个叠加。解释复杂系统（例如激发的苯阳离子）的超快非绝热电子振动过程仍然极具挑战性。在这里，报告了一个计算模型，其中非绝热事件在远离圆锥形交叉点的地方看到，并由涉及非相邻绝热态叠加的电子动力学控制。
The study of coupled electron-nuclear dynamics driven by coherent superpositions of electronic states is now possible in attosecond science experiments. The objective is to understand the electronic control of chemical reactivity. In this work we report coherent 8-state non-adiabatic electron-nuclear dynamics simulations of the benzene radical cation. The computations were inspired by the extreme ultraviolet (XUV) experimental results in which all 8 electronic states were prepared with significant population. Our objective was to study the nuclear dynamics using various bespoke coherent electronic state superpositions as initial conditions in the Quantum-Ehrenfest method. The original XUV measurements were supported by Multi-configuration time-dependent Hartree (MCTDH) simulations, which suggested a model of successive passage through conical intersections. The present computations support a complementary model where non-adiabatic events are seen far from a conical intersection and are controlled by electron dynamics involving non-adjacent adiabatic states. It proves to be possible to identify two superpositions that can be linked with two possible fragmentation paths. Interpreting ultrafast non-adiabatic vibronic processes of complex systems such as the excited benzene cation remains highly challenging. Here, a computational model is reported, where non-adiabatic events are seen far from a conical intersection and are controlled by electron dynamics involving a superposition of non-adjacent adiabatic states.
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影响因子：
2.9
作者：
Allan, Charlotte S. M.;Lasorne, Benjamin;Robb, Michael A.
通讯作者：
Robb, Michael A.
影响因子：
16.6
作者：
Galbraith MCE;Scheit S;Golubev NV;Reitsma G;Zhavoronkov N;Despré V;Lépine F;Kuleff AI;Vrakking MJJ;Kornilov O;Köppel H;Mikosch J
通讯作者：
Mikosch J
影响因子：
4.4
作者：
Kuleff, AI;Breidbach, J;Cederbaum, LS
通讯作者：
Cederbaum, LS
影响因子：
4.4
作者：
Jenkins, Andrew J.;Vacher, Morgane;Robb, Michael A.
通讯作者：
Robb, Michael A.
影响因子：
8.6
作者：
Breidbach, J;Cederbaum, LS
通讯作者：
Cederbaum, LS