Benchmark of excitation energy shifts from frozen-density embedding theory

• Verfasst von: Zech, Alexander [VerfasserIn]
• Verfasst von: Ricardi, Niccolò [VerfasserIn]
• Verfasst von: Prager, Stefan [VerfasserIn]
• Verfasst von: Dreuw, Andreas [VerfasserIn]
• Verfasst von: Wesolowski, Tomasz A. [VerfasserIn]
• Titel: Benchmark of excitation energy shifts from frozen-density embedding theory
• Titelzusatz: introduction of a density-overlap-based applicability threshold
• Verf.angabe: Alexander Zech, Niccolò Ricardi, Stefan Prager, Andreas Dreuw, and Tomasz A. Wesolowski
• E-Jahr: 2018
• Jahr: June 15, 2018
• Umfang: 13 S.
• Fussnoten: Gesehen am 17.03.2020
• Titel Quelle: Enthalten in: Journal of chemical theory and computation
• Ort Quelle: Washington, DC, 2004
• Jahr Quelle: 2018
• Band/Heft Quelle: 14(2018), 8, Seite 4028-4040
• ISSN Quelle: 1549-9626
• DOI: doi:10.1021/acs.jctc.8b00201
• Datenträger: Online-Ressource
• Sprache: eng
• K10plus-PPN: 1692703102

Abstract

We present a thorough investigation of the errors in results obtained with the combination of frozen-density embedding theory and the algebraic diagrammatic construction scheme for the polarization propagator of second order (FDE-ADC(2)). The study was carried out on a set of 52 intermolecular complexes with varying interaction strength, each consisting of a chromophore of fundamental interest and a few small molecules in its environment. The errors emerging in frozen-density embedding theory-based methods originate from (a) the solver of the quantum many-body problem used to obtain the embedded wave function (ΨAemb), (b) the approximation for the explicit density functional for the embedding potential, and (c) the choice of the density representing the environment (ρB(r⃗)). The present work provides a comprehensive analysis of the errors in the excitation energies based on the last two factors. Furthermore, a density-overlap-based parameter is proposed to be used as an a priori criterion of applicability.