2025/05/16 by Zhaohan Zhang, Zhang, Zhao-Han, Yang Li +9
Physics and Astronomy · #Advanced Chemical Physics Studies #Atomic Physics (physics.atom-ph) #Chemical Physics (physics.chem-ph) #FOS: Physical sciences #Laser-Matter Interactions and Applications #Quantum Physics (quant-ph) #Spectroscopy and Quantum Chemical Studies
paper · pdf · doi:10.48550/arxiv.2505.11290
openalex publication_date 2025/05/16 · openalex created_date 2025/10/10 · openalex updated_date 2026/08/03
We introduce a framework for resolving electron-hole dynamics within wavefunction-based multiconfigurational time-dependent Hartree-Fock (MCTDHF) theory. Central to this framework is a time-domain generalization of the extended Koopmans' theorem, which rigorously defines time-dependent hole states through single-electron removal. From this foundation, we prove the existence of exact equations of motion for time-dependent Dyson orbitals, enabling instantaneous construction of photofragments' reduced density matrices. The formalism further yields a systematic procedure to extract hole-resolved observables, such as channel-resolved photoelectron momentum distributions, directly from time-dependent ab initio wavefunctions. As a demonstration, we employ an attosecond ω-2ω laser strategy to control hole dynamics, thereby resolving a long-standing challenge in MCTDHF simulations. This advance opens a pathway for exploring correlated multielectron dynamics in atoms and molecules under ultrafast laser fields.