Fourth-order algebraic diagrammatic construction for electron detachment and attachment

• Verfasst von: Leitner, Jonas [VerfasserIn]
• Verfasst von: Dempwolff, Adrian [VerfasserIn]
• Verfasst von: Dreuw, Andreas [VerfasserIn]
• Titel: Fourth-order algebraic diagrammatic construction for electron detachment and attachment
• Titelzusatz: the IP- and EA-ADC(4) methods
• Verf.angabe: Jonas Leitner, Adrian L. Dempwolff, and Andreas Dreuw
• E-Jahr: 2024
• Jahr: 12 September 2024
• Umfang: 11 S.
• Illustrationen: Illustrationen
• Fussnoten: Online veröffentlicht: 30. August 2024 ; Gesehen am 18.09.2024
• Titel Quelle: Enthalten in: The journal of physical chemistry. A, Molecules, clusters, and aerosols
• Ort Quelle: Washington, DC : American Chemical Society, 1997
• Jahr Quelle: 2024
• Band/Heft Quelle: 128(2024), 36 vom: Sept., Seite 7680-7690
• ISSN Quelle: 1520-5215
• DOI: doi:10.1021/acs.jpca.4c03037
• Datenträger: Online-Ressource
• Sprache: eng
• K10plus-PPN: 1902908775

Abstract

We present a non-Dyson fourth-order algebraic diagrammatic construction formulation of the electron propagator, featuring the distinct IP- and EA-ADC(4) schemes for the treatment of ionization and electron attachment processes. The algebraic expressions have been derived automatically using the intermediate state representation approach and implemented in the Q-Chem quantum-chemical program package. The performance of the novel methods is assessed with respect to high-level reference data for ionization potentials and electron affinities of closed- and open-shell systems. While only minor improvements over the corresponding third-order methods are observed for one-hole ionization and one-particle electron attachment processes from closed-shell systems (MAEIP-ADC(4) = 0.27 eV and MAEEA-ADC(4) = 0.05 eV), a significantly enhanced performance is found in case of open-shell reference states (MAEIP-ADC(4) = 0.11 eV and MAEEA-ADC(4) = 0.02 eV). A particularly appealing feature of the novel methods is their accurate treatment of satellite transitions. For closed-shell reference states, we obtain accuracies of MAEIP-ADC(4) = 0.81 eV and MAEEA-ADC(4) = 0.27 eV, while in case of open-shell reference states, mean absolute errors of MAEIP-ADC(4) = 0.15 eV and MAEEA-ADC(4) = 0.27 eV are found.