{"title":"On the calculation of lanthanide systems. The spectral parameters of praseodymium trivalent ion","authors":"A. Toader, M. C. Buta, F. Cimpoesu","doi":"10.19261/cjm.2023.1146","DOIUrl":null,"url":null,"abstract":"In this work, taking the Pr(III) ion as a suitable case study, the authors test the capacity of a series of Gaussian Type Orbitals (GTOs) basis sets to account for the atomic spectra of lanthanide ions. An extended relevance of this assessment can be found in modeling the luminescence of lanthanide-based materials. It was selected the Pr(III) case because it shows a rather rich collection of experimental data, emerging from the f2 and fd configurations. The energy barycenters of spectral multiplets can be equated analytically in terms of the so-called Slater-Condon parameters. By multi-configurational ab initio procedures, with basis sets from existing GTO repositories, the calculated f→f transitions are moderately higher than the experimental values, while the relative energies of Fd states undergo both under- and over-estimation. The GTO shortcomings, that are impacting the accuracy, were debated, the critical perspective spreading the seeds of future development.","PeriodicalId":9922,"journal":{"name":"Chemistry Journal of Moldova","volume":null,"pages":null},"PeriodicalIF":0.5000,"publicationDate":"2023-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Chemistry Journal of Moldova","FirstCategoryId":"1085","ListUrlMain":"https://doi.org/10.19261/cjm.2023.1146","RegionNum":0,"RegionCategory":null,"ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q4","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
引用次数: 0
Abstract
In this work, taking the Pr(III) ion as a suitable case study, the authors test the capacity of a series of Gaussian Type Orbitals (GTOs) basis sets to account for the atomic spectra of lanthanide ions. An extended relevance of this assessment can be found in modeling the luminescence of lanthanide-based materials. It was selected the Pr(III) case because it shows a rather rich collection of experimental data, emerging from the f2 and fd configurations. The energy barycenters of spectral multiplets can be equated analytically in terms of the so-called Slater-Condon parameters. By multi-configurational ab initio procedures, with basis sets from existing GTO repositories, the calculated f→f transitions are moderately higher than the experimental values, while the relative energies of Fd states undergo both under- and over-estimation. The GTO shortcomings, that are impacting the accuracy, were debated, the critical perspective spreading the seeds of future development.
期刊介绍:
"Chemistry Journal of Moldova. General, Industrial and Ecological Chemistry" seeks to publish experimental or theoretical research results of outstanding significance and timeliness in all fields of Chemistry, including Industrial and Ecological Chemistry. The main goal of this edition is strengthening the Chemical Society of Moldova, following development of research in Moldovan chemical institutions and promotion of their collaboration with international chemical community. Manuscripts are welcome from all countries.