Nonoxido VIV complexes: Prediction of the EPR spectrum and electronic structure of simple coordination compounds and amavadin
Density functional theory (DFT) calculations of the 51V hyperfine coupling (HFC) tensor A have been completed for 20 "bare" VIV complexes with different donor sets, electric charges, and coordination geometries. Calculations were performed with ORCA and Gaussian software, using functionals...
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ftsassariuniiris:oai:iris.uniss.it:11388/175729 2024-04-14T08:18:01+00:00 Nonoxido VIV complexes: Prediction of the EPR spectrum and electronic structure of simple coordination compounds and amavadin Sanna, Daniele SCIORTINO, Giuseppe UGONE, Valeria MICERA, Giovanni GARRIBBA, Eugenio Sanna, Daniele Sciortino, Giuseppe Ugone, Valeria Micera, Giovanni Garribba, Eugenio 2016 http://hdl.handle.net/11388/175729 https://doi.org/10.1021/acs.inorgchem.6b00409 http://pubs.acs.org/journal/inocaj eng eng info:eu-repo/semantics/altIdentifier/wos/WOS:000380864900028 volume:55 issue:15 firstpage:7373 lastpage:7387 numberofpages:15 journal:INORGANIC CHEMISTRY http://hdl.handle.net/11388/175729 doi:10.1021/acs.inorgchem.6b00409 info:eu-repo/semantics/altIdentifier/scopus/2-s2.0-84979978498 http://pubs.acs.org/journal/inocaj Physical and Theoretical Chemistry Inorganic Chemistry info:eu-repo/semantics/article 2016 ftsassariuniiris https://doi.org/10.1021/acs.inorgchem.6b00409 2024-03-15T04:07:24Z Density functional theory (DFT) calculations of the 51V hyperfine coupling (HFC) tensor A have been completed for 20 "bare" VIV complexes with different donor sets, electric charges, and coordination geometries. Calculations were performed with ORCA and Gaussian software, using functionals BP86, TPSS0, B1LYP, PBE0, B3LYP, B3P, B3PW, O3LYP, BHandHLYP, BHandH, and B2PLYP. Among the basis sets, 6-311g(d,p), 6-311++g(d,p), VTZ, cc-pVTZ, def2-TZVPP, and the "core properties" CP(PPP) were tested. The experimental Aiso and Ai (where i = x or z, depending on the geometry and electronic structure of VIV complex) were compared with the values calculated by DFT methods. The results indicated that, based on the mean absolute percentage deviation (MAPD), the best functional to predict Aiso or Ai is the double hybrid B2PLYP. With this functional and the basis set VTZ, it is possible to predict the Aiso and Az of the EPR spectrum of amavadin with deviations of -1.1% and -2.0% from the experimental values. The results allowed us to divide the spectra of nonoxido VIV compounds in three types - called "type 1", "type 2", and "type 3", characterized by different composition of the singly occupied molecular orbital (SOMO) and relationship between the values of Ax, Ay, and Az. For "type 1" spectra, Az ≫ Ax ≈ Ay and Az is in the range of (135-155) × 10-4 cm-1 for "type 2" spectra, Ax ≈ Ay ≫ Az and Ax ≈ Ay are in the range of (90-120) × 10-4 cm-1 and for the intermediate spectra of "type 3", Az > Ay > Ax or Ax > Ay > Az, with Az or Ax values in the range of (120-135) × 10-4 cm-1. The electronic structure of the VIV species was also discussed, and the results showed that the values of Ax or Az are correlated with the percent contribution of V-dxy orbital in the SOMO. Similarly to VIVO species, for amavadin the SOMO is based mainly on the V-dxy orbital, and this accounts for the large experimental value of Az (153 × 10-4 cm-1). Article in Journal/Newspaper Orca CINECA IRIS Universitá Degli Studi di Sassari Inorganic Chemistry 55 15 7373 7387 |
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Open Polar |
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CINECA IRIS Universitá Degli Studi di Sassari |
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ftsassariuniiris |
language |
English |
topic |
Physical and Theoretical Chemistry Inorganic Chemistry |
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Physical and Theoretical Chemistry Inorganic Chemistry Sanna, Daniele SCIORTINO, Giuseppe UGONE, Valeria MICERA, Giovanni GARRIBBA, Eugenio Nonoxido VIV complexes: Prediction of the EPR spectrum and electronic structure of simple coordination compounds and amavadin |
topic_facet |
Physical and Theoretical Chemistry Inorganic Chemistry |
description |
Density functional theory (DFT) calculations of the 51V hyperfine coupling (HFC) tensor A have been completed for 20 "bare" VIV complexes with different donor sets, electric charges, and coordination geometries. Calculations were performed with ORCA and Gaussian software, using functionals BP86, TPSS0, B1LYP, PBE0, B3LYP, B3P, B3PW, O3LYP, BHandHLYP, BHandH, and B2PLYP. Among the basis sets, 6-311g(d,p), 6-311++g(d,p), VTZ, cc-pVTZ, def2-TZVPP, and the "core properties" CP(PPP) were tested. The experimental Aiso and Ai (where i = x or z, depending on the geometry and electronic structure of VIV complex) were compared with the values calculated by DFT methods. The results indicated that, based on the mean absolute percentage deviation (MAPD), the best functional to predict Aiso or Ai is the double hybrid B2PLYP. With this functional and the basis set VTZ, it is possible to predict the Aiso and Az of the EPR spectrum of amavadin with deviations of -1.1% and -2.0% from the experimental values. The results allowed us to divide the spectra of nonoxido VIV compounds in three types - called "type 1", "type 2", and "type 3", characterized by different composition of the singly occupied molecular orbital (SOMO) and relationship between the values of Ax, Ay, and Az. For "type 1" spectra, Az ≫ Ax ≈ Ay and Az is in the range of (135-155) × 10-4 cm-1 for "type 2" spectra, Ax ≈ Ay ≫ Az and Ax ≈ Ay are in the range of (90-120) × 10-4 cm-1 and for the intermediate spectra of "type 3", Az > Ay > Ax or Ax > Ay > Az, with Az or Ax values in the range of (120-135) × 10-4 cm-1. The electronic structure of the VIV species was also discussed, and the results showed that the values of Ax or Az are correlated with the percent contribution of V-dxy orbital in the SOMO. Similarly to VIVO species, for amavadin the SOMO is based mainly on the V-dxy orbital, and this accounts for the large experimental value of Az (153 × 10-4 cm-1). |
author2 |
Sanna, Daniele Sciortino, Giuseppe Ugone, Valeria Micera, Giovanni Garribba, Eugenio |
format |
Article in Journal/Newspaper |
author |
Sanna, Daniele SCIORTINO, Giuseppe UGONE, Valeria MICERA, Giovanni GARRIBBA, Eugenio |
author_facet |
Sanna, Daniele SCIORTINO, Giuseppe UGONE, Valeria MICERA, Giovanni GARRIBBA, Eugenio |
author_sort |
Sanna, Daniele |
title |
Nonoxido VIV complexes: Prediction of the EPR spectrum and electronic structure of simple coordination compounds and amavadin |
title_short |
Nonoxido VIV complexes: Prediction of the EPR spectrum and electronic structure of simple coordination compounds and amavadin |
title_full |
Nonoxido VIV complexes: Prediction of the EPR spectrum and electronic structure of simple coordination compounds and amavadin |
title_fullStr |
Nonoxido VIV complexes: Prediction of the EPR spectrum and electronic structure of simple coordination compounds and amavadin |
title_full_unstemmed |
Nonoxido VIV complexes: Prediction of the EPR spectrum and electronic structure of simple coordination compounds and amavadin |
title_sort |
nonoxido viv complexes: prediction of the epr spectrum and electronic structure of simple coordination compounds and amavadin |
publishDate |
2016 |
url |
http://hdl.handle.net/11388/175729 https://doi.org/10.1021/acs.inorgchem.6b00409 http://pubs.acs.org/journal/inocaj |
genre |
Orca |
genre_facet |
Orca |
op_relation |
info:eu-repo/semantics/altIdentifier/wos/WOS:000380864900028 volume:55 issue:15 firstpage:7373 lastpage:7387 numberofpages:15 journal:INORGANIC CHEMISTRY http://hdl.handle.net/11388/175729 doi:10.1021/acs.inorgchem.6b00409 info:eu-repo/semantics/altIdentifier/scopus/2-s2.0-84979978498 http://pubs.acs.org/journal/inocaj |
op_doi |
https://doi.org/10.1021/acs.inorgchem.6b00409 |
container_title |
Inorganic Chemistry |
container_volume |
55 |
container_issue |
15 |
container_start_page |
7373 |
op_container_end_page |
7387 |
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1796317400620072960 |