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Both approaches, dubbed amfX2C and e(xtended)amfX2C, allow us to uniquely tailor PCE corrections to mean-field models, viz. Hartree\u2013Fock or Kohn\u2013Sham DFT, in the latter case also avoiding the need for a point-wise calculation of exchange\u2013correlation PCE corrections. We assess the numerical performance of these PCE correction models on spinor energies of group 18 (closed-shell) and group 16 (open-shell) diatomic molecules, achieving a consistent \u224810\u22125 Hartree accuracy compared to reference four-component data. Additional tests include SCF calculations of molecular properties such as absolute contact density and contact density shifts in copernicium fluoride compounds (CnFn, n = 2,4,6), as well as equation-of-motion coupled-cluster calculations of x-ray core-ionization energies of 5d- and 6d-containing molecules, where we observe an excellent agreement with reference data. To conclude, we are confident that our (e)amfX2C PCE correction models constitute a fundamental milestone toward a universal and reliable relativistic two-component quantum-chemical approach, maintaining the accuracy of the parent four-component one at a fraction of its computational cost.<\/jats:p>","DOI":"10.1063\/5.0095112","type":"journal-article","created":{"date-parts":[[2022,9,19]],"date-time":"2022-09-19T11:20:53Z","timestamp":1663586453000},"update-policy":"https:\/\/doi.org\/10.1063\/aip-crossmark-policy-page","source":"Crossref","is-referenced-by-count":77,"title":["Exact two-component Hamiltonians for relativistic quantum chemistry: Two-electron picture-change corrections made simple"],"prefix":"10.1063","volume":"157","author":[{"ORCID":"https:\/\/orcid.org\/0000-0001-9818-2372","authenticated-orcid":false,"given":"Stefan","family":"Knecht","sequence":"first","affiliation":[{"name":"Algorithmiq Ltd 1 , Kanavakatu 3C, FI-00160 Helsinki, Finland"},{"name":"SHE Chemie, GSI Helmholtzzentrum f\u00fcr Schwerionenforschung GmbH 2 , Planckstr. 1, 64291 Darmstadt, Germany"},{"name":"Department of Chemistry, Johannes-Gutenberg Universit\u00e4t Mainz 3 , Duesbergweg 10-14, 55128 Mainz, Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-0776-4137","authenticated-orcid":false,"given":"Michal","family":"Repisky","sequence":"additional","affiliation":[{"name":"Hylleraas Centre for Quantum Molecular Sciences, Department of Chemistry, UiT\u2013The Arctic University of Norway 4 , N-9037 Troms\u00f8, Norway"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-8743-7381","authenticated-orcid":false,"given":"Hans J\u00f8rgen Aagaard","family":"Jensen","sequence":"additional","affiliation":[{"name":"Department of Physics, Chemistry and Pharmacy, University of Southern Denmark, Campusvej 55 5 , DK-5230 Odense M, Denmark"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-6407-0305","authenticated-orcid":false,"given":"Trond","family":"Saue","sequence":"additional","affiliation":[{"name":"Laboratoire de Chimie et Physique Quantiques (CNRS UMR 5626), Universit\u00e9 Toulouse III \u2013 Paul Sabatier 6 , 118 Route de Narbonne, F-31062 Toulouse Cedex, France"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"317","published-online":{"date-parts":[[2022,9,19]]},"reference":[{"key":"2023081006104523800_c1","volume-title":"Introduction to Relativistic Quantum Chemistry","year":"2007"},{"key":"2023081006104523800_c2","volume-title":"Relativistic Quantum Chemistry: The Fundamental Theory of Molecular Science","year":"2009"},{"key":"2023081006104523800_c3","doi-asserted-by":"publisher","first-page":"3077","DOI":"10.1002\/cphc.201100682","article-title":"Relativistic Hamiltonians for chemistry: A primer","volume":"12","year":"2011","journal-title":"ChemPhysChem"},{"key":"2023081006104523800_c4","doi-asserted-by":"publisher","first-page":"59","DOI":"10.1016\/j.physrep.2013.11.006","article-title":"Advances in relativistic molecular quantum mechanics","volume":"537","year":"2014","journal-title":"Phys. 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