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Calculations of hyperfine coupling constant of copper(II) in aqueous environment. Finite temperature molecular dynamics and relativistic effects

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Abstract

The presented paper is focused on the calculation of hyperfine coupling constants (HFCC) of Cu 2+ ion in water environment. To simulate the conditions of the electron paramagnetic resonance (EPR) experiment in aqueous phase, molecular dynamics using the density functional theory (DFT) was employed. In total three different functionals (BLYP, B3LYP, M06) were employed for studying their suitability in describing coordination of Cu 2+ by water molecules. The system of our interest was composed of one Cu 2+ cation surrounded by a selected number (between thirty and fifty) of water molecules. Besides the non-relativistic HFCCs (Fermi contact terms) of Cu 2+ also the four-component relativistic HFCC calculations are presented. The importance of the proper evaluation of HFCCs, the inclusion of spin-orbit term, for Cu 2+ containing systems (Neese, J. Chem. Phys. 118, 3939 2003; Almeida et al., Chem. Phys. 332, 176 2007) is confirmed at the relativistic four-component level of theory.

Five and six coordinated copper dication is solvated by adding extra water molecules to simulate conditions in aqueous solution. Molecular dynamics study is performed and nonrelativistic and relativistic hyperfine coupling constants are calculated subsequently.

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Acknowledgments

First of all, we are very grateful for help, valuable discussions and know-how (via providing the ReSpect code) to Vladimír G. Malkin, Oľga L. Malkina (Slovak Academy of Science) and Michal Repiský (University of Tromsø). The financial support was obtained from APVV (contract No. APVV-0202-10) and VEGA (contracts No. 1/0327/12 and 1/0765/14). We are grateful to the HPC center at the Slovak University of Technology in Bratislava, which is a part of the Slovak Infrastructure of High Performance Computing (SIVVP project, ITMS code 26230120002, funded by the European region development funds) for the computational time and resources made available.

Conflict of interests

The authors declare that they have no conflict of interest.

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Authors and Affiliations

  1. Institute of Physical Chemistry and Chemical Physics FCFT, Slovak University of Technology, Radlinskeho 9, Bratislava, SK-812 37, Slovakia

    Michal Malček, Lukáš Bučinský, Marián Valko & Stanislav Biskupič

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  1. Michal Malček
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  2. Lukáš Bučinský
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  3. Marián Valko
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  4. Stanislav Biskupič
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Correspondence to Michal Malček.

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Supplementary material

Supplementary material contains complete set of geometries from all the 300 K MDSs in the form of xyz files.

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Malček, M., Bučinský, L., Valko, M. et al. Calculations of hyperfine coupling constant of copper(II) in aqueous environment. Finite temperature molecular dynamics and relativistic effects. J Mol Model 21, 237 (2015). https://doi.org/10.1007/s00894-015-2752-8

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