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

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.

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Graphical Abstract 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.