Full Breit Hamiltonian in the Multiwavelets Framework

TL;DR

This paper extends the multiwavelet basis framework to accurately solve the 4-component Dirac-Coulomb-Breit Hamiltonian for core-electron spectroscopy, enabling precise calculations for complex materials and molecules.

Contribution

The authors develop a fully adaptive multiwavelet approach for the Dirac-Coulomb-Breit Hamiltonian, demonstrating its accuracy and potential for three-dimensional molecular and material applications.

Findings

Multiwavelets reproduce grid-based results with high precision.

Results are independent of nuclear model with tight error thresholds.

Magnetic and Gauge contributions from s-orbitals match experimental data.

Abstract

New techniques in core-electron spectroscopy are necessary to resolve the structures of oxides of $f$-elements and other strongly correlated materials that are present only as powders and not as single crystals. Thus, accurate quantum chemical methods need to be developed to calculate core spectroscopic properties in such materials. In this contribution, we present an important development in this direction, extending our fully adaptive real-space multiwavelet basis framework to tackle the 4-component Dirac-Coulomb-Breit Hamiltonian. We show that Multiwavelets are able to reproduce one-dimensional grid-based approaches. They are however a fully three-dimensional approach which can later on be extended to molecules and materials. Our Multiwavelet implementation attained precise results irrespective of the chosen nuclear model, provided that the error threshold is tight enough and the chosen polynomial basis is sufficiently large. Furthermore, our results confirmed that in two-electron species, the magnetic and Gauge contributions from $s$-orbitals are identical in magnitude and can account for the experimental evidence from $K$ and $L$ edges.