光电离引发的微分超快电荷迁移：分子对称性和互变异构形式的影响
Photo-ionization Initiated Differential Ultrafast Charge Migration: Impact of Molecular Symmetries and Tautomeric Forms
摘要：
光致电离诱导的超快电子动力学被认为是与分子解离相关的较慢的核动力学的前兆。在这里，使用从头算多电子波包传播方法，我们研究了整体的多电子动力学，引发的不同的互变异构体的原型分子具有一个以上的对称元素的外价轨道的电离。从每个系统的初始创建的平均空穴密度的时间演化，我们确定明显不同的电荷动力学响应的互变异构体。我们观察到，酮形式显示出远离与互变异构氢键合的氮的电荷迁移方向，而在烯醇中-远离与互变异构氢键合的氧。此外，不同对称性的分子轨道电离后的动力学表明，a'轨道与a”对称性相比，显示出快速和高度离域的电荷。这些观察结果表明，为什么不同的互变异构体不同的响应XUV电离，并可能解释随后不同的裂解途径。还提出了一个实验原理图，允许检测和重建这样的电荷动态。虽然本研究使用了一个简单的，典型的生物相关分子，它揭示了明确的作用，分子的对称性和互变异构的电离触发的电荷迁移，控制许多超快的物理，化学和生物过程，使互变异构形式的分子设计所需的电荷迁移的一个有前途的工具。
英文摘要：
Photo-ionization induced ultrafast electron dynamics is considered as a precursor to the slower nuclear dynamics associated with molecular dissociation. Here, using ab initio multielectron wave-packet propagation method, we study the overall many-electron dynamics, triggered by the ionization of outer-valence orbitals of different tautomers of a prototype molecule with more than one symmetry element. From the time evolution of the initially created averaged hole density of each system, we identify distinctly different charge dynamics response in the tautomers. We observe that keto form shows charge migration direction away from the nitrogen bonded with tautomeric hydrogen, while in enol - away from oxygen bonded to tautomeric hydrogen. Additionally, the dynamics following ionization of molecular orbitals of different symmetry reveal that a' orbitals show fast and highly delocalized charge in comparison to a" symmetry. These observations indicate why different tautomers respond differently to an XUV ionization, and might explain the subsequent different fragmentation pathways. An experimental schematics allowing detection and reconstruction of such charge dynamics is also proposed. Although the present study uses a simple, prototypical bio-relevant molecule, it reveals the explicit role of molecular symmetry and tautomerism in the ionization-triggered charge migration that controls many ultrafast physical, chemical, and biological processes, making tautomeric forms a promising tool of molecular design for desired charge migration.
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