title: Adapting algebraic diagrammatic construction schemes for the polarization propagator to problems with multi-reference electronic ground states exploiting the spin-flip ansatz.
abstract: For the investigation of molecular systems with electronic ground states exhibiting multi-reference character, a spin-flip (SF) version of the algebraic diagrammatic construction (ADC) scheme for the polarization propagator up to third order perturbation theory (SF-ADC(3)) is derived via the intermediate state representation and implemented into our existing ADC computer program adcman. The accuracy of these new SF-ADC(n) approaches is tested on typical situations, in which the ground state acquires multi-reference character, like bond breaking of H2 and HF, the torsional motion of ethylene, and the excited states of rectangular and square-planar cyclobutadiene. Overall, the results of SF-ADC(n) reveal an accurate description of these systems in comparison with standard multi-reference methods. Thus, the spin-flip versions of ADC are easy-to-use methods for the calculation of "few-reference" systems, which possess a stable single-reference triplet ground state.
authors.affiliation: Interdisciplinary Center for Scientific Computing, Ruprecht-Karls University, Im Neuenheimer Feld 368, 69120 Heidelberg, Germany.
authors.forename: Daniel
authors.initials: D
authors.lastname: Lefrancois
authors.affiliation: Interdisciplinary Center for Scientific Computing, Ruprecht-Karls University, Im Neuenheimer Feld 368, 69120 Heidelberg, Germany.
authors.forename: Michael
authors.initials: M
authors.lastname: Wormit
authors.affiliation: Interdisciplinary Center for Scientific Computing, Ruprecht-Karls University, Im Neuenheimer Feld 368, 69120 Heidelberg, Germany.
authors.forename: Andreas
authors.initials: A
authors.lastname: Dreuw