利用多参考代数图解构造理论模拟 Fe(CO)5 及其光解离产物的瞬态 X 射线光电子能谱
Simulating Transient X-ray Photoelectron Spectra of Fe(CO)5 and Its Photodissociation Products With Multireference Algebraic Diagrammatic Construction Theory
AI总结：
该研究采用 MR-ADC 方法模拟 Fe(CO)5 及其光解离产物的瞬态 XPS，揭示芯空穴屏蔽、自旋-轨道耦合和配体场分裂对化学位移的关键作用。
摘要：
对瞬态 X 射线光电子能谱（XPS）进行准确模拟，为在理解分子和材料中的光激发动力学时弥合理论与实验之间的差距提供了独特机会。然而，沿光化学反应路径模拟 X 射线光电子能谱具有挑战性，因为这需要准确描述电子结构，并在激发态或非平衡基态几何结构中纳入芯空穴屏蔽、轨道弛豫、电子相关以及自旋-轨道耦合。在本工作中，我们采用最近发展的多参考代数图解构造理论（MR-ADC），研究 Fe(CO)5 及其在 266 nm 光激发后的光解离产物（Fe(CO)4、Fe(CO)3）的芯电离态和 X 射线光电子能谱。纳入自旋-轨道耦合和高阶电子相关效应的模拟瞬态 Fe 3p 与 CO 3σ XPS 能谱，被证明与 Leitner 等人的实验测量结果［J. Chem. Phys. 149, 044307 (2018)］吻合良好。我们的计算表明，在重现实验观察到的羰基铁配合物瞬态 Fe 3p XPS 能谱中的化学位移时，芯空穴屏蔽、自旋-轨道耦合和配体场分裂效应具有同等重要性。我们的结果还证明，MR-ADC 方法在解释过渡金属化合物的瞬态 XPS 能谱方面可能非常有用。
英文摘要：
Accurate simulations of transient X-ray photoelectron spectra (XPS) provide unique opportunities to bridge the gap between theory and experiment in understanding the photoactivated dynamics in molecules and materials. However, simulating X-ray photoelectron spectra along a photochemical reaction pathway is challenging as it requires accurate description of electronic structure incorporating core-hole screening, orbital relaxation, electron correlation, and spin-orbit coupling in excited states or at nonequilibrium ground-state geometries. In this work, we employ the recently developed multireference algebraic diagrammatic construction theory (MR-ADC) to investigate the core-ionized states and X-ray photoelectron spectra of Fe(CO)5 and its photodissociation products (Fe(CO)4, Fe(CO)3) following excitation with 266 nm light. The simulated transient Fe 3p and CO 3σ XPS spectra incorporating spin-orbit coupling and high-order electron correlation effects are shown to be in a good agreement with the experimental measurements by Leitner et al. [J. Chem. Phys. 149, 044307 (2018)]. Our calculations suggest that core-hole screening, spin-orbit coupling, and ligand-field splitting effects are similarly important in reproducing the experimentally observed chemical shifts in transient Fe 3p XPS spectra of iron carbonyl complexes. Our results also demonstrate that the MR-ADC methods can be very useful in interpreting the transient XPS spectra of transition metal compounds.
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