First-Principles Calculation of <sup>1</sup>H NMR Chemical Shifts of Complex Metal Polyhydrides: The Essential Inclusion of Relativity and Dynamics
Abril C. Castro, David Balcells, Michal Repiský, Trygve Helgaker, Michele Cascella
Abstract
H NMR chemical shifts are strongly dependent on the relativistic treatment, the choice of the DFT exchange-correlation functional, and the conformational dynamics. By combining a fully relativistic four-component electronic-structure treatment with ab initio molecular dynamics, we were able to reliably model both the terminal and bridging hydride chemical shifts and to show that two NMR hydride signals were inversely assigned in the experiment.
Topics & Concepts
ChemistryChemical shiftTheory of relativityInclusion (mineral)MetalPhysical chemistryTheoretical physicsPhysicsOrganic chemistryMineralogyAdvanced Chemical Physics StudiesMolecular spectroscopy and chiralityCrystallography and molecular interactions