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Updated: Oct 29, 2025

Excitonic Hamiltonians for Calculating Optical Absorption Spectra and Optoelectronic Properties of Molecular Aggregates and Solids
Published on: May 27, 2020
All-order explicitly correlated relativistic computations for atoms and molecules
Péter Jeszenszki1, Dávid Ferenc1, Edit Mátyus1
1Institute of Chemistry, ELTE, Eötvös Loránd University, Pázmány Péter sétány 1/A, Budapest H-1117, Hungary.
Abstract:
A variational solution procedure is reported for the many-particle no-pair Dirac-Coulomb and Dirac-Coulomb-Breit Hamiltonians aiming at a parts-per-billion (ppb) convergence of the atomic and molecular energies, described within the fixed nuclei approximation. The procedure is tested for nuclear charge numbers from Z = 1 (hydrogen) to 28 (iron). Already for the lowest Z values, a significant difference is observed from leading-order Foldy-Woythusen perturbation theory, but the observed deviations are smaller than the estimated self-energy and vacuum polarization corrections.
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