The Spin-Flip Variant of the Algebraic-Diagrammatic Construction Yields the 
Correct Topology of S1/S0 Conical Intersections

Lefrancois, Daniel; Tuna, Deniz; Martínez, Todd J.; Dreuw, Andreas

doi:10.1021/acs.jctc.7b00634

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The Spin-Flip Variant of the Algebraic-Diagrammatic Construction Yields the Correct Topology of S₁/S₀ Conical Intersections

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Tuna, Deniz
Research Department Thiel, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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ct7b00634_si_001.pdf
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Citation

Lefrancois, D., Tuna, D., Martínez, T. J., & Dreuw, A. (2017). The Spin-Flip Variant of the Algebraic-Diagrammatic Construction Yields the Correct Topology of S₁/S₀ Conical Intersections. Journal of Chemical Theory and Computation, 13(9), 4436-4441. doi:10.1021/acs.jctc.7b00634.

Cite as: https://hdl.handle.net/11858/00-001M-0000-002E-0AE4-8

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.