Relativistic Density Functional NMR Tensors Analyzed with Spin‐free Localized Molecular Orbitals

Abstract

The implementation of fast relativistic methods based on density functional theory, in conjunction with localized molecular orbital (LMO) based analysis, allows straightforward interpretations of NMR parameters in terms of contributions from core shells, lone pairs, and bonds, for compounds containing elements from across the periodic table. We present a conceptual review of a frequently used LMO analysis of NMR parameters calculated in the presence of spin‐orbit interactions and other relativistic effects. An accompanying example focuses on the 15N shielding in a heavy metal complex.

Structure and bonding in rhodium coordination compounds: a 103Rh solid-state NMR and relativistic DFT study

“…103 Rh magnetic shielding tensors were analyzed in terms of contributions from NBOs and NLMOs, 127 according to previously published protocols. 75,128,129 These calculations were performed in AMS at the hybrid DFT (PBE0) and SO level for all isolated complexes and clusters of molecules, with other parameters identical to those described above. In each case, an initial set of canonical orbitals was calculated at the ZORA/SR level, followed by localization via the NBO 6.0 program included in the AMS package.…”

“…This can be accomplished, for instance, by consideration of contributions of suitably chosen sets of orbitals to the NMR interaction tensors. 74,75…”