Modern Quantum Chemistry Methodology for Predicting ³¹P Nuclear Magnetic Resonance Chemical Shifts

Phosphorus-31 nuclear magnetic resonance (³¹P NMR) spectroscopy is a powerful analytical physical chemistry experimental technique that is widely used to study the structure and dynamics of phosphorus-containing compounds today. Accurate calculation of ³¹P NMR chemical shifts lies in the basis of the proper assignment of NMR signals, as they can be closely spaced to each other in the NMR spectra of systems that bear nuclei with subtly different electron environments, like complex organophosphorus compounds, nucleic acids, and phosphates, etc. The most advanced quantum chemistry (QC) methods allow us to reach the agreement between theoretical values of ³¹P NMR chemical shifts and experiments within a few ppm, which makes them a useful tool for studying chemical structure, reaction mechanisms, and catalyst design with the aid of the NMR method. This review surveys the application of both density functional and wave function methods of electron structure to the calculation of ³¹P NMR chemical shifts and proposes a thorough discussion of the latest findings related to the factors affecting the final accuracy of the ³¹P NMR chemical shifts prediction, including basis sets, the geometry factor effect, solvent, vibrational, and relativistic corrections.