Assessment of approximate coupled-cluster and algebraic-diagrammatic-construction methods for ground- and excited-state reaction paths and the conical-intersection seam of a retinal-chromophore model

• Verfasst von: Tuna, Deniz [VerfasserIn]
• Verfasst von: Lefrancois, Daniel [VerfasserIn]
• Verfasst von: Dreuw, Andreas [VerfasserIn]
• Titel: Assessment of approximate coupled-cluster and algebraic-diagrammatic-construction methods for ground- and excited-state reaction paths and the conical-intersection seam of a retinal-chromophore model
• Verf.angabe: Deniz Tuna, Daniel Lefrancois, Łukasz Wolański, Samer Gozem, Igor Schapiro, Tadeusz Andruniów, Andreas Dreuw, and Massimo Olivucci
• Umfang: 24 S.
• Fussnoten: Gesehen am 13.12.2017
• Titel Quelle: Enthalten in: Journal of chemical theory and computation
• Jahr Quelle: 2015
• Band/Heft Quelle: 11(2015), 12, S. 5758-5781
• ISSN Quelle: 1549-9626
• DOI: doi:10.1021/acs.jctc.5b00022
• Datenträger: Online-Ressource
• Sprache: eng
• K10plus-PPN: 1566344662

Abstract

As a minimal model of the chromophore of rhodopsin proteins, the penta-2,4-dieniminium cation (PSB3) poses a challenging test system for the assessment of electronic-structure methods for the exploration of ground- and excited-state potential-energy surfaces, the topography of conical intersections, and the dimensionality (topology) of the branching space. Herein, we report on the performance of the approximate linear-response coupled-cluster method of second order (CC2) and the algebraic-diagrammatic-construction scheme of the polarization propagator of second and third orders (ADC(2) and ADC(3)). For the ADC(2) method, we considered both the strict and extended variants (ADC(2)-s and ADC(2)-x). For both CC2 and ADC methods, we also tested the spin-component-scaled (SCS) and spin-opposite-scaled (SOS) variants. We have explored several ground- and excited-state reaction paths, a circular path centered around the S1/S0 surface crossing, and a 2D scan of the potential-energy surfaces along the branching space.