论文标题
对称振动模式在相关驱动电荷迁移的脱水中的作用
The role of symmetric vibrational modes in the dehoherence of correlation-driven charge migration
论文作者
论文摘要
由于电子的相关性，从分子中快速去除电子可能会产生阳离子状态的连贯叠加，因此，这种方式启动了纯电子动力学，其中电离由电离留下的孔 - 电荷在整个系统中以超时时间尺度在整个系统中迁移。与核运动的耦合引入了一种反应，最终将电荷困住了，并且在口述领域中的关键问题是电子连贯性持续多长时间，以及哪些核自由度主要负责逆转。在这里，我们报告了胸肌外部价电离后的一致电子 - 核动力学的全维量子计算，这表明纯电子相干仅持续2-3 fs，然后在被核运动破坏之前。我们的分析表明，主要负责快速电子破坏的正常模式是对称的平面内模式。所有其他模式对电荷迁移几乎没有影响。该信息对于指导较大系统或搜索较长连贯时间的分子的降低模型的开发可能很有用。
Due to the electron correlation, a fast removal of an electron from a molecule may create a coherent superposition of cationic states and in this way initiate pure electronic dynamics in which the hole-charge left by ionization migrates throughout the system on an ultrashort time scale. The coupling to the nuclear motion introduces a decoherence that eventually traps the charge and a crucial question in the field of attochemistry is how long the electronic coherence lasts and which nuclear degrees of freedom are mostly responsible for the decoherence. Here, we report full-dimensional quantum calculations of the concerted electron-nuclear dynamics following outer-valence ionization of propynamide, which reveal that the pure electronic coherences last only 2-3 fs before being destroyed by the nuclear motion. Our analysis shows that the normal modes that are mostly responsible for the fast electronic decoherence are the symmetric in-plane modes. All other modes have little or no effect on the charge migration. This information can be useful to guide the development of reduced dimensionality models for larger systems or the search of molecules with long coherence times.
