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Accurate Relativistic Real-Time Time-Dependent Density Functional Theory for Valence and Core Attosecond Transient Absorption Spectroscopy

[Image: see text] First principles theoretical modeling of out-of-equilibrium processes observed in attosecond pump–probe transient absorption spectroscopy (TAS) triggering pure electron dynamics remains a challenging task, especially for heavy elements and/or core excitations containing fingerprint...

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Detalles Bibliográficos
Autores principales: Moitra, Torsha, Konecny, Lukas, Kadek, Marius, Rubio, Angel, Repisky, Michal
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2023
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9940299/
https://www.ncbi.nlm.nih.gov/pubmed/36757216
http://dx.doi.org/10.1021/acs.jpclett.2c03599
Descripción
Sumario:[Image: see text] First principles theoretical modeling of out-of-equilibrium processes observed in attosecond pump–probe transient absorption spectroscopy (TAS) triggering pure electron dynamics remains a challenging task, especially for heavy elements and/or core excitations containing fingerprints of scalar and spin–orbit relativistic effects. To address this, we formulate a methodology for simulating TAS within the relativistic real-time, time-dependent density functional theory (RT-TDDFT) framework, for both the valence and core energy regimes. Especially for TAS, full four-component (4c) RT simulations are feasible but computationally demanding. Therefore, in addition to the 4c approach, we also introduce the atomic mean-field exact two-component (amfX2C) Hamiltonian accounting for one- and two-electron picture-change corrections within RT-TDDFT. amfX2C preserves the accuracy of the parent 4c method at a fraction of its computational cost. Finally, we apply the methodology to study valence and near-L(2,3)-edge TAS processes of experimentally relevant systems and provide additional physical insights using relativistic nonequilibrium response theory.