Comparison of Density Functional and Correlated Wave Function Methods for the Prediction of Cu(II) Hyperfine Coupling Constants.

摘要: The reliable prediction of Cu(II) hyperfine coupling constants remains a challenge for quantum chemistry. Until recently only density functional theory (DFT) could target this property systems realistic size. However, wave function based methods become increasingly applicable. In the present work, we define large set complexes with experimentally known and use it to investigate performance modern chemical challenging spectroscopic parameter. DFT are evaluated against orbital-optimized second-order Moller-Plesset (OO-MP2) coupled cluster calculations including singles doubles excitations, driven by domain-based local pair natural orbital approach (DLPNO-CCSD). Special attention is paid definition basis that converges adequately toward limit given all considered in study, specifically optimized proposed purpose. results suggest can supplant but do not outcompete calculation constants. Mainstream hybrid functionals such as B3PW91 remain on average best choice.