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How accurate is density functional theory in predicting spin density? An insight from the prediction of hyperfine coupling constants

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Abstract

Electron paramagnetic resonance (EPR) spectroscopy has been proven to be an important technique for studying paramagnetic systems. Probably, the most accessible EPR parameter and the one that provides a significant amount of information about molecular structure and spin density is the hyperfine coupling constant (HFCC). Hence, accurate quantum-chemical modeling of HFCCs is frequently essential to the adequate interpretation of EPR spectra. It requires the precise spin density, which is the difference between the densities of α- and β-electrons, and thus, its quality is expected to reflect the quality of the total electron density. The question of which approximate exchange-correlation density functional yields sufficiently accurate HFCCs, and thus, the spin density remains open. To assess the performance of well-established density functionals for calculating HFCCs, we used a series of 26 small paramagnetic species and compared the obtained results to the CCSD reference values. The performance of DFT was also tested on EPR-studied o-semiquinone radical interacting with water molecules and Mg2+ cation. The HFCCs were additionally calculated by the DLPNO-CCSD method, and this wave function-based technique was found superior to all functionals we tested. Although some functionals were found, on average, to be fairly efficient, we found that the most accurate functional is system-dependent, and therefore, the DLPNO-CCSD method should be preferred for theoretical investigations of the HFCCs and spin density.

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Acknowledgments

This paper is dedicated to Professor Zdzisław Latajka, honoring his many contributions to chemistry, on the occasion of his 70th birthday.

Funding

This work was financially supported by the National Science Centre, Poland (Narodowe Centrum Nauki, nr rej. 2018/02/X/ST5/01186). All computations were performed using computers of the Wroclaw Center for Networking and Supercomputing (Grant No. 47).

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  1. Faculty of Chemistry, Wrocław University, ul. F. Joliot-Curie 14, 50-383, Wrocław, Poland

    Maciej Witwicki, Paulina K. Walencik & Julia Jezierska

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  1. Maciej Witwicki
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Correspondence to Maciej Witwicki.

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Witwicki, M., Walencik, P.K. & Jezierska, J. How accurate is density functional theory in predicting spin density? An insight from the prediction of hyperfine coupling constants. J Mol Model 26, 10 (2020). https://doi.org/10.1007/s00894-019-4268-0

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