Algebraic-diagrammatic construction scheme for the polarization propagator including ground-state coupled-cluster amplitudes. II. Static polarizabilities

• Verfasst von: Hodecker, Manuel [VerfasserIn]
• Verfasst von: Rehn, Dirk R. [VerfasserIn]
• Verfasst von: Norman, Patrick [VerfasserIn]
• Verfasst von: Dreuw, Andreas [VerfasserIn]
• Titel: Algebraic-diagrammatic construction scheme for the polarization propagator including ground-state coupled-cluster amplitudes. II. Static polarizabilities
• Verf.angabe: Manuel Hodecker, Dirk R. Rehn, Patrick Norman, and Andreas Dreuw
• E-Jahr: 2019
• Jahr: 01 May 2019
• Umfang: 11 S.
• Fussnoten: Gesehen am 16.12.2019
• Titel Quelle: Enthalten in: The journal of chemical physics
• Ort Quelle: Melville, NY : American Institute of Physics, 1933
• Jahr Quelle: 2019
• Band/Heft Quelle: 150(2019,17) Artikel-Nummer 174105, 11 Seiten
• ISSN Quelle: 1089-7690
• DOI: doi:10.1063/1.5081665
• Datenträger: Online-Ressource
• Sprache: eng
• K10plus-PPN: 1685611656

Abstract

The modification of the algebraic-diagrammatic construction (ADC) scheme for the polarization propagator using ground-state coupled-cluster (CC) instead of Møller-Plesset (MP) amplitudes, referred to as CC-ADC, is extended to the calculation of molecular properties, in particular, dipole polarizabilities. Furthermore, in addition to CC with double excitations (CCD), CC with single and double excitations (CCSD) amplitudes can be used, also in the second-order transition moments of the ADC(3/2) method. In the second-order CC-ADC(2) variants, the MP correlation coefficients occurring in ADC are replaced by either CCD or CCSD amplitudes, while in the F/CC-ADC(2) and F/CC-ADC(3/2) variants, they are replaced only in the second-order modified transition moments. These newly implemented variants are used to calculate the static dipole polarizability of several small- to medium-sized molecules, and the results are compared to the ones obtained by full configuration interaction or experiment. It is shown that the results are consistently improved by the use of CC amplitudes, in particular, for aromatic systems such as benzene or pyridine, which have proven to be difficult cases for standard ADC approaches. In this case, the second-order CC-ADC(2) and F/CC-ADC(2) variants yield significantly better results than the standard third-order ADC(3/2) method, at a computational cost amounting to only about 1% of the latter.