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Title: Accuracy of Density Functional Theory Methods for the Calculation of Magnetic Exchange Couplings in Binuclear Iron(III) Complexes

Abstract

We assess the performance of popular hybrid density functional approximations for the prediction of magnetic exchange couplings (J) in FeIII complexes. To this end, eleven dinuclear oxo-bridged iron(III) complexes with accurately determined J values were chosen to cover cases of weak and strong antiferromagnetic couplings ranging from -6 cm -1 to -132 cm -1. Six representative exchange-correlation functionals ranging from the hybrids PBE and B3LYP to meta hybrids (M06, M062X), range separated functionals (HSE, LC-!PBE), and LSDA with 30 % of HF exchange were used for this assessment. These functionals have been suggested as good performers for this particular property in transition metal complexes and hence this assessment aims to narrow the interval of con dence for the particular case of Fe complexes. In addition, we examined the performance of an alternative method based on di erential local spin rotations to calculate magnetic exchange coupling parameters in these complexes. Our results show that, although some of these functionals perform on par, the M06 and HSE functionals yields magnetic exchange couplings in closer agreement with experimental data, with a mean absolute percentage errors of 8.6 and 9.2 %, respectively.

Authors:
 [1];  [1];  [2];  [2];  [1];  [1]
  1. Central Michigan Univ., Mount Pleasant, MI (United States). Dept. of Physics and Science of Advanced Materials
  2. Univ. of Florida, Gainesville, FL (United States). Dept. of Chemistry
Publication Date:
Research Org.:
Central Michigan Univ., Mount Pleasant, MI (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division
OSTI Identifier:
1577229
Grant/Contract Number:  
SC0018331
Resource Type:
Accepted Manuscript
Journal Name:
Polyhedron
Additional Journal Information:
Journal Volume: 176; Journal ID: ISSN 0277-5387
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Magnetic exchange couplings; DFT; Fe complexes

Citation Formats

Joshi, Rajendra P., Phillips, Jordan J., Mitchell, Kylie J., Christou, George, Jackson, Koblar A., and Peralta, Juan E. Accuracy of Density Functional Theory Methods for the Calculation of Magnetic Exchange Couplings in Binuclear Iron(III) Complexes. United States: N. p., 2019. Web. doi:10.1016/j.poly.2019.114194.
Joshi, Rajendra P., Phillips, Jordan J., Mitchell, Kylie J., Christou, George, Jackson, Koblar A., & Peralta, Juan E. Accuracy of Density Functional Theory Methods for the Calculation of Magnetic Exchange Couplings in Binuclear Iron(III) Complexes. United States. doi:10.1016/j.poly.2019.114194.
Joshi, Rajendra P., Phillips, Jordan J., Mitchell, Kylie J., Christou, George, Jackson, Koblar A., and Peralta, Juan E. Sat . "Accuracy of Density Functional Theory Methods for the Calculation of Magnetic Exchange Couplings in Binuclear Iron(III) Complexes". United States. doi:10.1016/j.poly.2019.114194.
@article{osti_1577229,
title = {Accuracy of Density Functional Theory Methods for the Calculation of Magnetic Exchange Couplings in Binuclear Iron(III) Complexes},
author = {Joshi, Rajendra P. and Phillips, Jordan J. and Mitchell, Kylie J. and Christou, George and Jackson, Koblar A. and Peralta, Juan E.},
abstractNote = {We assess the performance of popular hybrid density functional approximations for the prediction of magnetic exchange couplings (J) in FeIII complexes. To this end, eleven dinuclear oxo-bridged iron(III) complexes with accurately determined J values were chosen to cover cases of weak and strong antiferromagnetic couplings ranging from -6 cm-1 to -132 cm-1. Six representative exchange-correlation functionals ranging from the hybrids PBE and B3LYP to meta hybrids (M06, M062X), range separated functionals (HSE, LC-!PBE), and LSDA with 30 % of HF exchange were used for this assessment. These functionals have been suggested as good performers for this particular property in transition metal complexes and hence this assessment aims to narrow the interval of con dence for the particular case of Fe complexes. In addition, we examined the performance of an alternative method based on di erential local spin rotations to calculate magnetic exchange coupling parameters in these complexes. Our results show that, although some of these functionals perform on par, the M06 and HSE functionals yields magnetic exchange couplings in closer agreement with experimental data, with a mean absolute percentage errors of 8.6 and 9.2 %, respectively.},
doi = {10.1016/j.poly.2019.114194},
journal = {Polyhedron},
number = ,
volume = 176,
place = {United States},
year = {2019},
month = {11}
}

Journal Article:
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This content will become publicly available on November 30, 2020
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