BWs-ADC: The algebraic diagrammatic construction for the polarization propagator using a size-consistent Brillouin-Wigner partitioning up to third order in perturbation theory.

Authors

Linus Bjarne Dittmer, Adrian Johannes Müller, Jonas Leitner, Adrian Ludwig Dempwolff, Andreas Dreuw

Published in

The Journal of chemical physics. Volume 165. Issue 9. Sep 07, 2026.

Abstract

We present the algebraic diagrammatic construction for the polarization propagator (PP-ADC) formulated with a two-parameter, size-consistent Brillouin-Wigner partitioning (BWs) up to third order in perturbation theory (BWs-ADC). The resulting method is size-consistent, size-extensive, and regular and extends the applicability of ADC to systems with degenerate electronic ground states. We demonstrate that the secular matrices of BWs-ADC(2) and BWs-ADC(3) are structurally equivalent to their Møller-Plesset (MP-ADC) counterparts and determine optimal regularization parameters by analyzing the dissociation of H2 in a minimal basis. These parameters are subsequently refined using a benchmark set of 122 single excitations comprising both valence and Rydberg states. BWs-ADC(2) favors strong regularization in the occupied space, whereas virtual-space regularization is found to significantly increase excitation energy errors. In contrast, BWs-ADC(3) generally benefits from slight de-regularization. Both methods achieve a mean absolute error (MAE) of 0.15 eV, representing a substantial improvement over the corresponding MP-ADC approaches; for BWs-ADC(3), this error is dominated by a small number of outliers, whereas BWs-ADC(2) exhibits more uniform accuracy. A second benchmark demonstrates that parameter-optimized BWs-ADC methods also yield significantly improved oscillator strengths and excited-state dipole moments. Overall, BWs-ADC provides improved accuracy for single-reference systems while simultaneously extending the applicability of ADC to few-reference regimes, including bond dissociation processes, diradical species, and selected transition metal complexes.

PMID:
42678211
Bibliographic data and abstract were imported from PubMed on 01 Sep 2026.

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