Journal
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
Volume 11, Issue 12, Pages 5758-5781Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acs.jctc.5b00022
Keywords
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Funding
- Heidelberg Graduate School Mathematical and Computational Methods for the Sciences [GSC 220]
- Polish Ministry of Science and Higher Education for the Faculty of Chemistry of Wroclaw University of Technology
- National Science Foundation [CHE-1152070, CHE-1551416]
- Human Frontier Science Program Organization [RGP0049/2012CHE09-56776]
- Division Of Chemistry
- Direct For Mathematical & Physical Scien [1152070] Funding Source: National Science Foundation
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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 S-1/S-0 surface crossing, and a 21) scan of the potential-energy surfaces along the branching space. We find that the CC2 and ADC methods yield a different dimensionality of the intersection space. While the ADC methods yield a linear intersection topology, we find a conical intersection topology for the CC2 method. We present computational evidence showing that the linear-response CC2 method yields a surface crossing between the reference state and the first response state featuring characteristics that are expected for a true conical intersection. Finally, we test the performance of these methods for the approximate geometry optimization of the S-1/S-0 minimum-energy conical intersection and compare the geometries with available data from multireference methods. The present study provides new insight into the performance of linear-response CC2 and polarization-propagator ADC methods for molecular electronic spectroscopy and applications in computational photochemistry.
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