Malmö University Publications
Change search
CiteExportLink to record
Permanent link

Direct link
Cite
Citation style
  • apa
  • ieee
  • modern-language-association-8th-edition
  • vancouver
  • Other style
More styles
Language
  • de-DE
  • en-GB
  • en-US
  • fi-FI
  • nn-NO
  • nn-NB
  • sv-SE
  • Other locale
More languages
Output format
  • html
  • text
  • asciidoc
  • rtf
Natural Orbitals and Targeted Non-Orthogonal Orbital Sets for Atomic Hyperfine Structure Multiconfiguration Calculations
Malmö University, Faculty of Technology and Society (TS), Department of Materials Science and Applied Mathematics (MTM). Inst Appl Phys & Computat Math, Beijing 100088, Peoples R China; Fudan Univ, Inst Modern Phys, Dept Nucl Sci & Technol, Key Lab Nucl Phys & Ion Beam Applicat, Shanghai 200433, Peoples R China.ORCID iD: 0009-0006-0227-8120
Malmö University, Faculty of Technology and Society (TS), Department of Materials Science and Applied Mathematics (MTM). Fudan Univ, Inst Modern Phys, Dept Nucl Sci & Technol, Key Lab Nucl Phys & Ion Beam Applicat, Shanghai 200433, Peoples R China.ORCID iD: 0000-0001-5147-0094
Univ Libre Bruxelles, Spect Quantum Chem & Atmospher Remote Sensing, B-1050 Brussels, Belgium.
Vilnius Univ, Inst Theoret Phys & Astron, LT-010222 Vilnius, Lithuania.ORCID iD: 0000-0003-0039-1163
Show others and affiliations
2024 (English)In: Atoms, E-ISSN 2218-2004, Vol. 12, no 6, article id 30Article in journal (Refereed) Published
Abstract [en]

Hyperfine structure constants have many applications, but are often hard to calculate accurately due to large and canceling contributions from different terms of the hyperfine interaction operator, and also from different closed and spherically symmetric core subshells that break up due to electron correlation effects. In multiconfiguration calculations, the wave functions are expanded in terms of configuration state functions (CSFs) built from sets of one-electron orbitals. The orbital sets are typically enlarged within the layer-by-layer approach. The calculations are energy-driven, and orbitals in each new layer of correlation orbitals are spatially localized in regions where the weighted total energy decreases the most, overlapping and breaking up different closed core subshells in an irregular pattern. As a result, hyperfine structure constants, computed as expectation values of the hyperfine operators, often show irregular or oscillating convergence patterns. Large orbital sets, and associated large CSF expansions, are needed to obtain converged values of the hyperfine structure constants. We analyze the situation for the states of the {2s22p3,2s22p23p,2s22p24p} odd and {2s22p23s,2s2p4,2s22p24s,2s22p23d} even configurations in N I, and show that the convergence with respect to the increasing sets of orbitals is radically improved by introducing separately optimized orbital sets targeted for describing the spin- and orbital-polarization effects of the 1s and 2s core subshells that are merged with, and orthogonalized against, the ordinary energy-optimized orbitals. In the layer-by-layer approach, the spectroscopic orbitals are kept frozen from the initial calculation and are not allowed to relax in response to the introduced layers of correlation orbitals. To compensate for this lack of variational freedom, the orbitals are transformed to natural orbitals prior to the final calculation based on single and double substitutions from an increased multireference set. The use of natural orbitals has an important impact on the states of the 2s22p23s configuration, bringing the corresponding hyperfine interaction constants in closer agreement with experiment. Relying on recent progress in methodology, the multiconfiguration calculations are based on configuration state function generators, cutting down the time for spin-angular integration by factors of up to 50, compared to ordinary calculations.

Place, publisher, year, edition, pages
MDPI, 2024. Vol. 12, no 6, article id 30
Keywords [en]
variational methods, multiconfiguration Dirac-Hartree-Fock, atomic properties, targeted orbitals, non-orthogonal orbital sets, natural orbitals, convergence, hyperfine structure
National Category
Physical Sciences
Identifiers
URN: urn:nbn:se:mau:diva-70037DOI: 10.3390/atoms12060030ISI: 001254682700001Scopus ID: 2-s2.0-85196811769OAI: oai:DiVA.org:mau-70037DiVA, id: diva2:1886513
Available from: 2024-08-01 Created: 2024-08-01 Last updated: 2024-08-01Bibliographically approved

Open Access in DiVA

fulltext(386 kB)96 downloads
File information
File name FULLTEXT01.pdfFile size 386 kBChecksum SHA-512
116039eec337c85e24c07ae7aa02fd8423a1c07ff827a965f8017d82e734d2be754096bc60b9c91dea986946fcf8d4fa9ee4daaeca270a909b33869b5ded168c
Type fulltextMimetype application/pdf

Other links

Publisher's full textScopus

Authority records

Li, YantingJönsson, Per

Search in DiVA

By author/editor
Ma, MingxuanLi, YantingGaigalas, GediminasLi, JiguangChen, ChongyangJönsson, Per
By organisation
Department of Materials Science and Applied Mathematics (MTM)
In the same journal
Atoms
Physical Sciences

Search outside of DiVA

GoogleGoogle Scholar
Total: 97 downloads
The number of downloads is the sum of all downloads of full texts. It may include eg previous versions that are now no longer available

doi
urn-nbn

Altmetric score

doi
urn-nbn
Total: 189 hits
CiteExportLink to record
Permanent link

Direct link
Cite
Citation style
  • apa
  • ieee
  • modern-language-association-8th-edition
  • vancouver
  • Other style
More styles
Language
  • de-DE
  • en-GB
  • en-US
  • fi-FI
  • nn-NO
  • nn-NB
  • sv-SE
  • Other locale
More languages
Output format
  • html
  • text
  • asciidoc
  • rtf