Hermitian second-order methods for excited electronic states

• Verfasst von: Hodecker, Manuel [VerfasserIn]
• Verfasst von: Rehn, Dirk R. [VerfasserIn]
• Verfasst von: Dreuw, Andreas [VerfasserIn]
• Titel: Hermitian second-order methods for excited electronic states
• Titelzusatz: unitary coupled cluster in comparison with algebraic-diagrammatic construction schemes
• Verf.angabe: Manuel Hodecker, Dirk R. Rehn and Andreas Dreuw
• E-Jahr: 2020
• Jahr: 02 March 2020
• Umfang: 12 S.
• Fussnoten: Gesehen am 31.03.2020
• Titel Quelle: Enthalten in: The journal of chemical physics
• Ort Quelle: Melville, NY : American Institute of Physics, 1933
• Jahr Quelle: 2020
• Band/Heft Quelle: 152(2020,9) Artikel-Nummer 094106, 12 Seiten
• ISSN Quelle: 1089-7690
• DOI: doi:10.1063/1.5142354
• Datenträger: Online-Ressource
• Sprache: eng
• Sach-SW: body perturbation-theory
• Sach-SW: correlated molecular calculations
• Sach-SW: doubles model
• Sach-SW: fock space
• Sach-SW: full configuration-interaction
• Sach-SW: gaussian-basis sets
• Sach-SW: linear-response
• Sach-SW: polarization propagator
• Sach-SW: quantum-chemistry
• Sach-SW: triplet excitation-energies
• K10plus-PPN: 1693579839

Abstract

Employing an intermediate state representation (ISR) approach, Hermitian second-order methods for the calculation of electronic excitation energies are presented and compared in detail. These comprise the algebraic-diagrammatic construction scheme for the polarization propagator, a hybrid second-order ISR scheme based on traditional coupled-cluster theory as well as two similar approaches based on a unitary coupled-cluster (UCC) ansatz. Although in a strict perturbation-theoretical framework all prove to be identical, differences emerge when the corresponding converged cluster amplitudes are used and depending on how the similarity-transformed UCC Hamiltonian is evaluated. The resulting excitation energies, however, do not significantly differ for systems well described by means of perturbation theory.