Nuclear Magnetic Resonance Spectroscopy and Quantum Chemical Calculations

Nuclear magnetic resonance (NMR) spectroscopy is a powerful analytical technique that probes the magnetic properties of atomic nuclei to reveal molecular structure, dynamics and interactions. By applying a static magnetic field and radiofrequency pulses, NMR measures resonance frequencies that depend sensitively on the electronic environment surrounding each nucleus. Quantum chemical calculations, in particular those based on density functional theory (DFT) and post-Hartree-Fock methods, complement experimental NMR by predicting chemical shifts, coupling constants and shielding tensors from first principles. The combination of high-resolution NMR with advanced computational models has transformed fields as diverse as drug discovery, materials science and environmental analysis. Recent methodological advances include the treatment of relativistic effects for heavy elements, the incorporation of explicit solvent models, and the accurate simulation of paramagnetic systems. Together, experimental spectroscopy and quantum chemical prediction enable quantitative benchmarks for bond covalency, dynamic processes and non-covalent interactions, underpinning a deeper understanding of molecular function and guiding the design of new compounds with tailored properties.

Research from Nature Portfolio

Recent studies have demonstrated exceptional insight into actinide bonding by combining high-field ^15N NMR spectroscopy with relativistic quantum chemical analysis to reveal that uranium(VI)–nitride triple bonds exhibit unprecedented covalency and chemical shift anisotropy, reshaping the parameter space for metal–nitrogen correlations. In a separate investigation, systematic DFT benchmarking of proton and carbon chemical shifts in an azo-dye tautomer series has identified optimal functional and basis-set combinations for accurate prediction of solution-state NMR spectra, highlighting the critical influence of molecular geometry optimisation on ^1H- and ^13C-shift accuracy and guiding best practices in computational protocol development.

Nuclear Magnetic Resonance Spectroscopy and Quantum Chemical Calculations publication trend

The graph below shows the total number of articles in nuclear magnetic resonance spectroscopy and quantum chemical calculations across all publications each year (not limited to Nature Index journals).

Technical terms

Nuclear Magnetic Resonance (NMR) Spectroscopy: A technique that measures the resonance frequencies of nuclear spins in a magnetic field to derive structural and dynamic information about molecules.

Density Functional Theory (DFT): A quantum chemical approach that approximates the electronic energy of a system as a functional of its electron density, widely used to predict NMR parameters.

Chemical Shift Anisotropy: The directional dependence of the nuclear magnetic shielding tensor, giving rise to orientation-dependent resonance frequencies in solids and aligned samples.

Covalency: The degree of shared electron density between atoms in a bond, often quantified by correlating bond order with computed or observed NMR chemical shifts.

Paramagnetic Shift: A change in NMR resonance frequency induced by unpaired electron spins, requiring specialised theoretical treatment to predict accurately.

References

1. 31P Nuclear Magnetic Resonance Spectroscopy as a Probe of Thorium–Phosphorus Bond Covalency: Correlating Phosphorus Chemical Shift to Metal–Phosphorus Bond Order. Journal of the American Chemical Society (2023).
2. Tris-Silanide f‑Block Complexes: Insights into Paramagnetic Influence on NMR Chemical Shifts. JACS Au (2024).
3. 13 C carbene nuclear magnetic resonance chemical shift analysis confirms Ce IV [double bond, length as m-dash]C double bonding in cerium( iv )–diphosphonioalkylidene complexes. Chemical Science (2023).
4. Exceptional uranium(VI)-nitride triple bond covalency from 15N nuclear magnetic resonance spectroscopy and quantum chemical analysis. Nature Communications (2021).
5. DFT calculations of 1H- and 13C-NMR chemical shifts of 3-methyl-1-phenyl-4-(phenyldiazenyl)-1H-pyrazol-5-amine in solution. Scientific Reports (2022).