The spin-flip variant of the algebraic-diagrammatic construction yields the correct topology of S1/S0 conical intersections

• Verfasst von: Lefrancois, Daniel [VerfasserIn]
• Verfasst von: Dreuw, Andreas [VerfasserIn]
• Titel: The spin-flip variant of the algebraic-diagrammatic construction yields the correct topology of S1/S0 conical intersections
• Verf.angabe: Daniel Lefrancois, Deniz Tuna, Todd J. Martínez, and Andreas Dreuw
• Umfang: 6 S.
• Fussnoten: Im Titel erscheinen die Ziffern 1 und 0 tiefgestellt. ; Gesehen am 13.12.2017
• Titel Quelle: Enthalten in: Journal of chemical theory and computation
• Jahr Quelle: 2017
• Band/Heft Quelle: 13(2017), 9, S. 4436-4441
• ISSN Quelle: 1549-9626
• DOI: doi:10.1021/acs.jctc.7b00634
• Datenträger: Online-Ressource
• Sprache: eng
• K10plus-PPN: 1566348579

Abstract

While the conventional variants of the algebraic-diagrammatic construction (ADC) scheme for the polarization propagator are generally incapable of correctly describing the topology of S1/S0 conical intersections (CIs), its corresponding spin-flip (SF) variant of third-order ADC (ADC(3)) is herein demonstrated to successfully reproduce the S1/S0 minimum-energy CI (MECI) of twisted formaldinium (H2C═NH2+). Analytical nuclear excited-state gradients of ADC have been used in combination with the CIOpt program for the optimization of the MECI without the need for nonadiabatic-coupling vectors. For comparison, MS-CASPT2 calculations were performed via conventional CI optimization employing analytical nonadiabatic-coupling vectors. It is shown that SF-ADC(3) yields the correct dimensionality of the CI and overall compares very favorably to the MS-CASPT2 results.