Role of Valence and Semicore Electron Correlation on Spin Gaps in Fe(II)-Porphyrins

[Image: see text] The role of valence and semicore correlation in differentially stabilizing the intermediate spin state of Fe(II)-porphyrins is analyzed. For CASSCF treatments of valence correlation, a (32,34) active space containing metal 3d, d′ orbitals and the entire π system of the porphyrin is...

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Autores principales: Li Manni, Giovanni, Kats, Daniel, Tew, David P., Alavi, Ali
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2019
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6728061/
https://www.ncbi.nlm.nih.gov/pubmed/30681852
http://dx.doi.org/10.1021/acs.jctc.8b01277
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author Li Manni, Giovanni
Kats, Daniel
Tew, David P.
Alavi, Ali
author_facet Li Manni, Giovanni
Kats, Daniel
Tew, David P.
Alavi, Ali
author_sort Li Manni, Giovanni
collection PubMed
description [Image: see text] The role of valence and semicore correlation in differentially stabilizing the intermediate spin state of Fe(II)-porphyrins is analyzed. For CASSCF treatments of valence correlation, a (32,34) active space containing metal 3d, d′ orbitals and the entire π system of the porphyrin is necessary to stabilize the intermediate spin state. Semicore correlation provides a minor (−1.6 kcal/mol) but quantitatively significant correction. Accounting for valence, semicore, and correlation beyond the active space enlarges the ((3)E(g)–(5)A(1g)) spin gap to −5.7 kcal/mol.
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spelling pubmed-67280612019-09-06 Role of Valence and Semicore Electron Correlation on Spin Gaps in Fe(II)-Porphyrins Li Manni, Giovanni Kats, Daniel Tew, David P. Alavi, Ali J Chem Theory Comput [Image: see text] The role of valence and semicore correlation in differentially stabilizing the intermediate spin state of Fe(II)-porphyrins is analyzed. For CASSCF treatments of valence correlation, a (32,34) active space containing metal 3d, d′ orbitals and the entire π system of the porphyrin is necessary to stabilize the intermediate spin state. Semicore correlation provides a minor (−1.6 kcal/mol) but quantitatively significant correction. Accounting for valence, semicore, and correlation beyond the active space enlarges the ((3)E(g)–(5)A(1g)) spin gap to −5.7 kcal/mol. American Chemical Society 2019-01-25 2019-03-12 /pmc/articles/PMC6728061/ /pubmed/30681852 http://dx.doi.org/10.1021/acs.jctc.8b01277 Text en Copyright © 2019 American Chemical Society This is an open access article published under a Creative Commons Attribution (CC-BY) License (http://pubs.acs.org/page/policy/authorchoice_ccby_termsofuse.html) , which permits unrestricted use, distribution and reproduction in any medium, provided the author and source are cited.
spellingShingle Li Manni, Giovanni
Kats, Daniel
Tew, David P.
Alavi, Ali
Role of Valence and Semicore Electron Correlation on Spin Gaps in Fe(II)-Porphyrins
title Role of Valence and Semicore Electron Correlation on Spin Gaps in Fe(II)-Porphyrins
title_full Role of Valence and Semicore Electron Correlation on Spin Gaps in Fe(II)-Porphyrins
title_fullStr Role of Valence and Semicore Electron Correlation on Spin Gaps in Fe(II)-Porphyrins
title_full_unstemmed Role of Valence and Semicore Electron Correlation on Spin Gaps in Fe(II)-Porphyrins
title_short Role of Valence and Semicore Electron Correlation on Spin Gaps in Fe(II)-Porphyrins
title_sort role of valence and semicore electron correlation on spin gaps in fe(ii)-porphyrins
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6728061/
https://www.ncbi.nlm.nih.gov/pubmed/30681852
http://dx.doi.org/10.1021/acs.jctc.8b01277
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