Spin-dependent terms of the Breit-Pauli Hamiltonian evaluated with an explicitly correlated Gaussian basis set for molecular computations

Fuente: arXiv
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Main Authors: Jeszenszki, Péter, Hollósy, Péter, Margócsy, Ádám, Mátyus, Edit
Format: Preprint
Published: 2025
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author Jeszenszki, Péter
Hollósy, Péter
Margócsy, Ádám
Mátyus, Edit
author_facet Jeszenszki, Péter
Hollósy, Péter
Margócsy, Ádám
Mátyus, Edit
contents This work collects the spin-dependent leading-order relativistic and quantum-electrodynamical corrections for the electronic structure of atoms and molecules within the non-relativistic quantum electrodynamics framework. We report the computation of perturbative corrections using an explicitly correlated Gaussian basis set, which allows high-precision computations for few-electron systems. In addition to numerical tests for triplet Be, triplet H$_2$, and triplet H$_3^+$ states and comparison with no-pair Dirac-Coulomb-Breit Hamiltonian energies, numerical results are reported for electronically excited states of the helium dimer, He$_2$, for which the present implementation delivers high-precision magnetic coupling curves necessary for a quantitative understanding of the fine structure of its high-resolution rovibronic spectrum.
format Preprint
id arxiv_https___arxiv_org_abs_2506_19131
institution arXiv
publishDate 2025
record_format arxiv
spellingShingle Spin-dependent terms of the Breit-Pauli Hamiltonian evaluated with an explicitly correlated Gaussian basis set for molecular computations
Jeszenszki, Péter
Hollósy, Péter
Margócsy, Ádám
Mátyus, Edit
Chemical Physics
This work collects the spin-dependent leading-order relativistic and quantum-electrodynamical corrections for the electronic structure of atoms and molecules within the non-relativistic quantum electrodynamics framework. We report the computation of perturbative corrections using an explicitly correlated Gaussian basis set, which allows high-precision computations for few-electron systems. In addition to numerical tests for triplet Be, triplet H$_2$, and triplet H$_3^+$ states and comparison with no-pair Dirac-Coulomb-Breit Hamiltonian energies, numerical results are reported for electronically excited states of the helium dimer, He$_2$, for which the present implementation delivers high-precision magnetic coupling curves necessary for a quantitative understanding of the fine structure of its high-resolution rovibronic spectrum.
title Spin-dependent terms of the Breit-Pauli Hamiltonian evaluated with an explicitly correlated Gaussian basis set for molecular computations
topic Chemical Physics
url https://arxiv.org/abs/2506.19131