Keeping two electronic states at a small fixed energy gap, the tube algorithm finds approximate minimum energy conical intersections, and CCSD versions of these structures match CASSCF and SF-TDDFT reference geometries for three molecules.
Generalized coupled cluster theory for ground and excited state intersections
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abstract
Coupled cluster theory in the standard formulation is unable to correctly describe conical intersections among states of the same symmetry. This limitation has restricted the practical application of an otherwise highly accurate electronic structure model, particularly in nonadiabatic dynamics. Recently, the intersection problem among the excited states was fully characterized and resolved. However, intersections with the ground state remain an open challenge, and addressing this problem is our objective here. We present a generalized coupled cluster framework that correctly accounts for the geometric phase effect and avoids bifurcations of the solutions to the ground state equations. Several applications are presented that demonstrate the correct description of ground state conical intersections. We also propose how the framework can be used for other electronic-structure methods.
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physics.chem-ph 1years
2024 1verdicts
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Determining minimum energy conical intersections by enveloping the seam: exploring ground and excited state intersections in coupled cluster theory
Keeping two electronic states at a small fixed energy gap, the tube algorithm finds approximate minimum energy conical intersections, and CCSD versions of these structures match CASSCF and SF-TDDFT reference geometries for three molecules.