溶液中光电子能谱与光电子圆二色性的可极化嵌入方法：水合丙氨酸的芯能级电离
Polarizable Embedding for Photoelectron Spectroscopy and Photoelectron Circular Dichroism in Solution: Core-Level Ionization of Aqueous Alanine
- Scuola Normale Superiore（比萨高等师范学院）
- Università degli Studi di Trieste（的里雅斯特大学）
机构由 AI 辅助整理，请以论文原文为准。
AI总结：
该研究提出可极化量子力学/分子力学方法，结合 fluctuating-charge 力场，成功模拟水合丙氨酸的光电子能谱与圆二色性，证实需同时考虑溶剂结构与环境极化以可靠建模溶液中光电子可观测量。
AI中文摘要：
我们提出一种可极化量子力学/分子力学方法，用于计算溶液中分子光电离可观测量。该方法将束缚态与连续态电子的静态交换密度泛函理论处理，与通过 fluctuating-charge 力场描述的全原子可极化嵌入耦合；fluctuating charges 与基态量子力学密度自洽确定，随后被纳入静态交换哈密顿量以描述出射电子。我们验证了该耦合方案的数值性能，并将其应用于水溶液中两性离子 L-丙氨酸的 X 射线光电子能谱及光电子圆二色性计算，采用从分子动力学提取的构型系综。计算得到的谱图与实验曲线吻合极佳，表明需同时处理原子级溶剂结构与环境极化，才能可靠模拟水溶液中的光电子可观测量。
英文摘要：
We present a polarizable quantum-mechanics/molecular-mechanics formulation for the calculation of molecular photoionization observables in solution. The approach couples the static-exchange density-functional-theory treatment of bound and continuum electronic states with a fully atomistic polarizable embedding described with the fluctuating-charge force-field. The fluctuating charges are determined self-consistently with the ground-state quantum-mechanical density and are subsequently included in the static-exchange Hamiltonian to account for the outgoing electron. The numerical behavior of the coupled scheme is validated and applied to the X-ray photoelectron spectrum and photoelectron circular dichroism of zwitterionic L-alanine in aqueous solution, using an ensemble of configurations extracted from molecular dynamics. Calculated spectra reproduce experimental profiles remarkably well, demonstrating that atomistic solvent structure and environmental polarization must be treated together to reliably model photoelectron observables in aqueous solution.
