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

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 sta...

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Bibliographic Details
Published in:Journal of chemical theory and computation 2019-03, Vol.15 (3), p.1492-1497
Main Authors: Li Manni, Giovanni, Kats, Daniel, Tew, David P, Alavi, Ali
Format: Article
Language:English
Subjects:
Electron spin
Letter
Porphyrins
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Summary: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.
ISSN:1549-9618
1549-9626
DOI:10.1021/acs.jctc.8b01277