AI 中文总结
本文通过含时组态相互作用方法，揭示水溶液金属离子芯激发时CTTS特性的实时演化机制，明确了相关实验探测的特征，为溶液中CTTS态的时间分辨研究提供了理论依据。
AI 中文摘要
溶剂电荷转移（CTTS）激发是溶液中生成水合电子、引发氧化还原反应的核心化学途径，但CTTS的最早阶段——激发态本身的形成——通常被视为瞬时过程。本文从时域视角研究水溶液金属离子的芯级光激发过程中CTTS特性的构建机制，采用含时组态相互作用方法模拟密集芯激发态流形的相干演化，追踪电子电荷从初始局部位点向溶剂支撑终态的超快转移过程。研究发现，随着电荷在多个耦合组态中扩散，动力学行为从少数态的振荡演变为有效不可逆的离域，为CTTS特性的早期出现提供了微观机制。本文结果对芯级光谱学和芯空穴时钟型测量在溶液中的探测对象给出了清晰的实时解释，明确了在芯空穴寿命时间尺度上探测CTTS态构建的实验特征。展望未来，X射线自由电子激光的阿秒及亚飞秒X射线泵浦-探测方法为直接时间分辨溶液中芯激发CTTS波包提供了可行途径。
英文摘要
Charge-transfer-to-solvent (CTTS) excitations provide a chemically central route to generating hydrated electrons and initiating redox chemistry in solution, yet the earliest stage of CTTS---the formation of the excited state itself---is usually treated as instantaneous. Here we present a time-domain perspective of how CTTS character builds up during core-level photoexcitation of an aqueous metal ion. Using time-dependent configuration interaction, we simulate the coherent evolution of a dense manifold of core-excited states and track the ultrafast flow of electronic charge from the initially localized site into solvent-supported final states. We find that the dynamics evolves from a few-state, oscillatory behavior to effectively irreversible delocalization, as the charge disperses among many coupled configurations, providing a microscopic mechanism for the early-time emergence of CTTS character. Our results offer a transparent real-time interpretation of what core-level spectroscopies and core-hole-clock-type measurements can probe in solutions, outlining experimental signatures for probing the build-up of CTTS states on the core-hole-lifetime timescale. Looking ahead, attosecond and sub-femtosecond X-ray pump--probe approaches at X-ray free-electron lasers provide a realistic route to directly time-resolve the core-excited CTTS wave packets in solution.
