Chapter 8: Relativistic Calculations of Nuclear Magnetic Resonance Parameters

Relativistic effects are important for the accurate evaluation of the observables of nuclear magnetic resonance (NMR) spectroscopy, the nuclear magnetic shielding and the indirect spin–spin coupling tensors. Some of the most notable relativistic effects, in particular for light elements in the vicinity of heavy nuclei, are due to spin–orbit effects, an effect difficult to evaluate when starting from a non-relativistic wavefunction. Two- and four-component relativistic methods include spin–orbit effects variationally, and the recent improvements in the computational efficiency of these methods open new opportunities for accurate calculations of NMR parameters also for molecules with heavy elements. We here present an overview of the different approximations that have been introduced for calculating relativistic effects with two- and four-component methods and how these methods can be used to calculate the NMR parameters. We will also give some examples of systems that have been studied computationally with two- and four-component relativistic methods and discuss the importance of relativistic effects on the shielding and indirect spin–spin coupling constants.