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arXiv · 2608.25669

Benchmark of Multi-Channel Dyson Equation and Algebraic Diagrammatic Construction Methods for molecules

Mike Keizer·Stefano Paggi·J. Arjan Berger·Pina Romaniello·Arno Förster
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Abstract

The Dyson-algebraic diagrammatic construction (ADC) and the multi-channel Dyson equation (MCDE) formalisms explicitly leverage multi-particle channels to formulate correlated theories of the single-particle Green's function that produce positive semi-definite spectral functions by construction. While the MCDE is strictly rooted in the Dyson formalism, most ADC calculations are performed in the non-Dyson (nD) framework that decouples electron attachment and detachment sectors. We benchmark the Dyson-ADC(2)-X [that is equivalent to the (3,1)-MCDE] and ADC(3) approximations on a set of 58 ionization potentials of 23 small molecules for which near-full configuration interaction reference data exist. Comparison of Dyson- to nD-ADC(3) reveals deviations of the order of 0.1 eV between both methods, calling into question the reliability of the nD approximation. We show that Dyson-ADC gives similar accuracy for first IPs as for semi-valence and semi-core transitions. Finally, we also benchmark the screened (3,1)-MCDE that screens all ladder interactions, and show that it improves over its unscreened counterpart.

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Mike Keizer, Stefano Paggi, J. Arjan Berger, Pina Romaniello, Arno Förster. 2026-08-26. Benchmark of Multi-Channel Dyson Equation and Algebraic Diagrammatic Construction Methods for molecules. https://arxiv.org/abs/2608.25669

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