Related Experiment Video
Updated: Aug 18, 2026

Line Shape Analysis of Dynamic NMR Spectra for Characterizing Coordination Sphere Rearrangements at a Chiral Rhenium Polyhydride Complex
Published on: July 27, 2022
Leading-order relativistic effects on nuclear magnetic resonance shielding tensors
Pekka Manninen1, Kenneth Ruud, Perttu Lantto
1Laboratory of Physical Chemistry, Department of Chemistry, University of Helsinki, Finland. manninen@chem.helsinki.fi
Abstract:
We present perturbational ab initio calculations of the nuclear-spin-dependent relativistic corrections to the nuclear magnetic resonance shielding tensors that constitute, together with the other relativistic terms reported by us earlier, the full leading-order perturbational set of results for the one-electron relativistic contributions to this observable, based on the (Breit-)Pauli Hamiltonian. These contributions are considered for the H(2)X (X = O,S,Se,Te,Po) and HX (X = F,Cl,Br,I,At) molecules, as well as the noble gas (Ne, Ar, Kr, Xe, Rn) atoms. The corrections are evaluated using the relativistic and magnetic operators as perturbations on an equal footing, calculated using analytical linear and quadratic response theory applied on top of a nonrelativistic reference state provided by self-consistent field calculations. The (1)H and heavy-atom nuclear magnetic shielding tensors are compared with four component, nearly basis-set-limit Dirac-Hartree-Fock calculations that include positronic excitations, as well as available literature data. Besides the easy interpretability of the different contributions in terms of familiar nonrelativistic concepts, the accuracy of the present perturbational scheme is striking for the isotropic part of the shielding tensor, for systems including elements up to Xe.
More Related Videos
14:55Atomic Scale Structural Studies of Macromolecular Assemblies by Solid-state Nuclear Magnetic Resonance Spectroscopy
Published on: September 17, 2017
09:25NMR 15N Relaxation Experiments for the Investigation of Picosecond to Nanoseconds Structural Dynamics of Proteins
Published on: November 1, 2024
Related Concept Videos
Diamagnetic Shielding of Nuclei: Local Diamagnetic Current
π Electron Effects on Chemical Shift: Overview
The Energies of Atomic Orbitals
π Electron Effects on Chemical Shift: Aromatic and Antiaromatic Compounds
Atomic Radii and Effective Nuclear Charge
¹H NMR: Interpreting Distorted and Overlapping Signals
As Δν decreases and the signals move closer, the doublets appear increasingly distorted. The intensities of the inner lines increase at the cost of those of the outer lines as the signals are slanted or...