Journal of Chemical Theory and Computation
Journal of Chemical Theory and Computation
4 years ago

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

The Spin-Flip Variant of the Algebraic-Diagrammatic Construction Yields the Correct Topology of S1/S0 Conical Intersections
Andreas Dreuw, Deniz Tuna, Todd J. Martínez, Daniel Lefrancois
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.

Publisher URL: http://dx.doi.org/10.1021/acs.jctc.7b00634

DOI: 10.1021/acs.jctc.7b00634

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