Jove
Visualize
Contact Us
JoVE
x logofacebook logolinkedin logoyoutube logo
ABOUT JoVE
OverviewLeadershipBlogJoVE Help Center
AUTHORS
Publishing ProcessEditorial BoardScope & PoliciesPeer ReviewFAQSubmit
LIBRARIANS
TestimonialsSubscriptionsAccessResourcesLibrary Advisory BoardFAQ
RESEARCH
JoVE JournalMethods CollectionsJoVE Encyclopedia of ExperimentsArchive
EDUCATION
JoVE CoreJoVE BusinessJoVE Science EducationJoVE Lab ManualFaculty Resource CenterFaculty Site
Terms & Conditions of Use
Privacy Policy
Policies

Related Concept Videos

Diamagnetic Shielding of Nuclei: Local Diamagnetic Current01:14

Diamagnetic Shielding of Nuclei: Local Diamagnetic Current

848
An applied magnetic field causes the electrons present in the molecule to circulate, setting up a local diamagnetic current within the molecule. The local diamagnetic current arising from circulating sigma-bonding electrons induces a magnetic field, Blocal that opposes the applied magnetic field, B0. The effective magnetic field experienced by these nuclei is given by the difference between the applied and local magnetic fields in a phenomenon called local diamagnetic shielding. Essentially,...
848
π Electron Effects on Chemical Shift: Overview01:27

π Electron Effects on Chemical Shift: Overview

1.1K
An applied magnetic field causes loosely bound π-electrons in organic molecules to circulate, producing a local or induced diamagnetic field over a large spatial volume. As the molecules tumble in solution, the field generated by π-electrons in spherical substituents results in a zero net field. However, the net field generated by π-electrons in non-spherical substituents is not zero. The effect of this induced field depends on the orientation of the molecule with respect to B0,...
1.1K
π Electron Effects on Chemical Shift: Aromatic and Antiaromatic Compounds01:14

π Electron Effects on Chemical Shift: Aromatic and Antiaromatic Compounds

1.2K
In aromatic compounds, such as benzene, the circulation of (4n + 2) π-electrons sets up a diamagnetic or diatropic ring current around the perimeter of the molecule. This current induces a magnetic field that opposes the external field inside the ring and reinforces it on the outside. The protons in benzene are deshielded and exhibit high chemical shifts in the range 6.5–8.5 ppm. The shielding effect at the center of the ring is evident in complex aromatic molecules, such as...
1.2K
¹H NMR: Interpreting Distorted and Overlapping Signals01:02

¹H NMR: Interpreting Distorted and Overlapping Signals

1.0K
Spin systems where the difference in chemical shifts of the coupled nuclei is greater than ten times J are called first-order spin systems. These nuclei are weakly coupled, and their chemical shifts and coupling constant can generally be estimated from the well-separated signals in the spectrum.
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...
1.0K
NMR Spectroscopy of Aromatic Compounds01:14

NMR Spectroscopy of Aromatic Compounds

4.7K
Aromatic compounds can be identified or analyzed using proton NMR and carbon‐13 NMR. Typically, aromatic hydrogens or hydrogens directly bonded to the aromatic rings are strongly deshielded by the aromatic ring current. Therefore, they absorb in the range of 6.5–8.0 ppm in proton NMR spectra. For instance, aromatic hydrogens directly bonded to the benzene ring absorb at 7.3 ppm. However, aromatic hydrogens of larger rings absorb farther upfield or downfield than the ideal range.
4.7K
NMR Spectroscopy: Chemical Shift Overview01:15

NMR Spectroscopy: Chemical Shift Overview

1.5K
The position of the absorption signal of a sample is reported relative to the position of the signal of tetramethylsilane (TMS), which is added as an internal reference while recording spectra. The difference between the absorption frequencies of the sample and TMS (in Hz) is divided by the spectrometer operating frequency (in MHz) to obtain a dimensionless quantity called the chemical shift. It is reported on the δ (delta) scale and expressed in parts per million.
For instance, the proton...
1.5K

You might also read

Related Articles

Articles linked to this work by shared authors, journal, and citation graph.

Sort by
Same author

A Benchmark and Basis-Set Extrapolation Study of Hyperfine Coupling Constants from the Random Phase Approximation and σ-Functionals.

The journal of physical chemistry. A·2026
Same author

A detailed comparison of ΔSCF methods with the constraint-based orbital-optimized excited state method.

Communications chemistry·2026
Same author

Formulation of an Efficient <math><mi>O</mi></math>(<i>M</i><sup>4</sup>)-Scaling Explicitly Correlated MP2-F12 Correction by Combining Numerical Quadrature with Density Fitting and CABS-RI.

Journal of chemical theory and computation·2026
Same author

Automated Discovery of Reactive Events via Hypergraph Mining of Ab Initio Atomistic Simulations.

Journal of chemical theory and computation·2026
Same author

Surface properties of Ga-Cu based liquid-metal alloys: impact of Cu dilution, topography, and alloy liquefaction.

RSC applied interfaces·2026
Same author

Analyzing the response of exchange-correlation potentials of chain-like molecules to electric fields by Kohn-Sham inversion and evaluation of the response within the random phase approximation.

The Journal of chemical physics·2025
Same journal

Complementing Onsager's Conductivity Theory by Grotthuss Mechanism Mitigation via Ion-Induced Depletion of Hydrogen-Bond-Donating Water.

Journal of chemical theory and computation·2026
Same journal

Microscopic Stress in Biomembranes: A Perspective on Key Concepts, Methods, and Applications.

Journal of chemical theory and computation·2026
Same journal

Analytic Nuclear Gradients Including Oriented External Electric Fields in a Molecule-Fixed Frame.

Journal of chemical theory and computation·2026
Same journal

Knowledge Distillation of a Protein Language Model Yields a Foundational Implicit Solvent Model.

Journal of chemical theory and computation·2026
Same journal

Generalizable Protein Folding Pathway Exploration with DA2-GRASP: Extending Beyond Miniproteins.

Journal of chemical theory and computation·2026
Same journal

Improving PCM in Protic Media: Markov State Models for TD-DFT Calculations.

Journal of chemical theory and computation·2026
See all related articles

Related Experiment Video

Updated: Jun 22, 2025

Line Shape Analysis of Dynamic NMR Spectra for Characterizing Coordination Sphere Rearrangements at a Chiral Rhenium Polyhydride Complex
10:52

Line Shape Analysis of Dynamic NMR Spectra for Characterizing Coordination Sphere Rearrangements at a Chiral Rhenium Polyhydride Complex

Published on: July 27, 2022

2.7K

Accurate NMR Shieldings with σ-Functionals.

Steffen Fauser1, Viktoria Drontschenko2, Christian Ochsenfeld2,3

  • 1Lehrstuhl für Theoretische Chemie, Universität Erlangen-Nürnberg, Egerlandstr. 3, D-91058 Erlangen, Germany.

Journal of Chemical Theory and Computation
|July 5, 2024
PubMed
Summary
This summary is machine-generated.

New sigma-functionals offer highly accurate predictions for nuclear magnetic resonance (NMR) shieldings. These advanced density-functional methods also excel at calculating reaction energies, demonstrating their universal applicability.

More Related Videos

Measuring Interactions of Globular and Filamentous Proteins by Nuclear Magnetic Resonance Spectroscopy NMR and Microscale Thermophoresis MST
10:28

Measuring Interactions of Globular and Filamentous Proteins by Nuclear Magnetic Resonance Spectroscopy NMR and Microscale Thermophoresis MST

Published on: November 2, 2018

12.1K
Atomic Scale Structural Studies of Macromolecular Assemblies by Solid-state Nuclear Magnetic Resonance Spectroscopy
14:55

Atomic Scale Structural Studies of Macromolecular Assemblies by Solid-state Nuclear Magnetic Resonance Spectroscopy

Published on: September 17, 2017

15.4K

Related Experiment Videos

Last Updated: Jun 22, 2025

Line Shape Analysis of Dynamic NMR Spectra for Characterizing Coordination Sphere Rearrangements at a Chiral Rhenium Polyhydride Complex
10:52

Line Shape Analysis of Dynamic NMR Spectra for Characterizing Coordination Sphere Rearrangements at a Chiral Rhenium Polyhydride Complex

Published on: July 27, 2022

2.7K
Measuring Interactions of Globular and Filamentous Proteins by Nuclear Magnetic Resonance Spectroscopy NMR and Microscale Thermophoresis MST
10:28

Measuring Interactions of Globular and Filamentous Proteins by Nuclear Magnetic Resonance Spectroscopy NMR and Microscale Thermophoresis MST

Published on: November 2, 2018

12.1K
Atomic Scale Structural Studies of Macromolecular Assemblies by Solid-state Nuclear Magnetic Resonance Spectroscopy
14:55

Atomic Scale Structural Studies of Macromolecular Assemblies by Solid-state Nuclear Magnetic Resonance Spectroscopy

Published on: September 17, 2017

15.4K

Area of Science:

  • Computational Chemistry
  • Quantum Chemistry
  • Density Functional Theory

Background:

  • Recent advancements in density-functional theory (DFT) have introduced fifth-rung correlation functionals, known as σ-functionals.
  • σ-Functionals are computationally similar to the random phase approximation but offer superior accuracy for energies in main group chemistry.
  • These functionals have shown promise in outperforming double-hybrid functionals for calculating reaction and transition state energies.

Purpose of the Study:

  • To systematically evaluate the accuracy of σ-functionals in describing nuclear magnetic resonance (NMR) shieldings.
  • To determine if σ-functionals, optimized solely on energy data, can accurately predict response properties like NMR shieldings.
  • To compare the performance of σ-functionals against other DFT methods, including double-hybrid functionals, for NMR shielding calculations.

Main Methods:

  • Implementation and application of σ-functionals for calculating NMR shieldings.
  • Utilized Kohn-Sham calculations with the Perdew-Burke-Ernzerhof (PBE) exchange-correlation functional for input orbitals and eigenvalues.
  • Systematic investigation and comparison of NMR shielding results across various DFT methods.

Main Results:

  • σ-Functionals yield highly accurate NMR shieldings, despite not being explicitly optimized for such properties.
  • The σ-functional, when combined with PBE orbitals, produced the most accurate NMR shieldings among all tested DFT methods.
  • This accuracy was achieved even when compared to methods employing double-hybrid functionals.

Conclusions:

  • σ-Functionals demonstrate universal applicability, accurately predicting both energies and response properties like NMR shieldings.
  • Their ability to provide reliable results for both energy and property calculations makes them versatile 'all-purpose' functionals.
  • The findings highlight the potential of σ-functionals as a powerful and accurate tool for various chemical applications.