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Multicomponent wavefunction-in-DFT embedding for positronium molecules
Stockholm University, Faculty of Science, Department of Physics. Universidad Nacional de Colombia, Colombia.ORCID iD: 0000-0001-9701-2099
Number of Authors: 22023 (English)In: Journal of Chemical Physics, ISSN 0021-9606, E-ISSN 1089-7690, Vol. 158, no 13, article id 134101Article in journal (Refereed) Published
Abstract [en]

This work presents an extension of the projector operator embedding scheme of Manby et al. [J. Chem. Theory Comput. 8, 2564 (2012)] in a multicomponent (MC) framework. Here, a molecular system containing electrons and other types of quantum species is divided into a wavefunction (WF) subsystem of interest and a density functional theory (DFT) environment. The WF-in-DFT partition decreases computational costs by partially truncating the WF subsystem basis set at the cost of introducing a controllable embedding error. To explore the applicability of the MC extension, third-order propagator-in-DFT calculations were performed for positron–anion complexes for alkoxides and carboxylates with carbon chains of different sizes. For these systems, it was found that selecting a WF subsystem with the positron and only the oxygen atoms caused an error of 0.1 eV or lower in positron-binding energies, while reducing between 33% and 55% the basis set size. The reduction of computational costs achieved with the embedding scheme allowed us to improve molecular positron-binding energy predictions by performing complete basis set limit extrapolations. Combining the WF-in-DFT embedding and the complete basis set extrapolation, positronium aliphatic alkoxides were predicted to be energetically stable by 0.3 eV with respect to Ps emission. Similarly, positronium carboxylates, both aromatic and aliphatic, were predicted to be stable by 1.3 eV.

Place, publisher, year, edition, pages
2023. Vol. 158, no 13, article id 134101
National Category
Physical Chemistry
Identifiers
URN: urn:nbn:se:su:diva-220200DOI: 10.1063/5.0139813ISI: 000970038800035PubMedID: 37031104Scopus ID: 2-s2.0-85152066812OAI: oai:DiVA.org:su-220200DiVA, id: diva2:1792128
Available from: 2023-08-28 Created: 2023-08-28 Last updated: 2023-08-28Bibliographically approved

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Moncada, Felix

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