EPR Spectroscopy of Cu(II) Complexes: Prediction of g-Tensors Using Double-Hybrid Density Functional Theory

Computational electron paramagnetic resonance (EPR) spectroscopy is an important field of applied quantum chemistry that contributes greatly to connecting spectroscopic observations with the fundamental description electronic structure for open-shell molecules. However, not all EPR parameters can be predicted accurately and reliably chemical systems. Among transition metal ions, Cu(II) centers in inorganic biology, their associated properties such as hyperfine coupling g-tensors, pose exceptional difficulties levels chemistry. In present work, we approach problem g-tensor calculations using double-hybrid density functional theory (DHDFT). Using a reference set 18 structurally spectroscopically characterized complexes, evaluate wide range modern functionals (DHDFs) have been previously this problem. Our results suggest current generation DHDFs consistently systematically outperform other computational approaches. The B2GP-PLYP PBE0-DH are singled out best on average prediction g-tensors. performance different discussed suggestions made practical applications future methodological developments.