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Spin–Spin Coupling Constant: Overview01:08

Spin–Spin Coupling Constant: Overview

1.0K
In bromoethane, the three methyl protons are coupled to the two methylene protons that are three bonds away. In accordance with the n+1 rule, the signal from the methyl protons is split into three peaks with 1:2:1 relative intensities. The methylene protons appear as a quartet, with the relative intensities of 1:3:3:1.
Qualitatively, any spin plus-half nucleus polarizes the spins of its electrons to the minus-half state. Consequently, the paired electron in the hydrogen–carbon bond must...
1.0K
Spin–Spin Coupling: Two-Bond Coupling (Geminal Coupling)01:20

Spin–Spin Coupling: Two-Bond Coupling (Geminal Coupling)

1.1K
Two NMR-active nuclei bonded to a central atom can be involved in geminal or two-bond coupling. Geminal coupling is commonly seen between diastereotopic protons in chiral molecules and unsymmetrical alkenes, among others.
The central atom need not be NMR-active because its electrons are affected by the electron polarization of the spin-active atoms. However, spin information is transmitted less effectively than in one-bond coupling, and 2J values are usually weaker than 1J values. The energy of...
1.1K
Spin–Spin Coupling: One-Bond Coupling01:17

Spin–Spin Coupling: One-Bond Coupling

1.1K
Coupling interactions are strongest between NMR-active nuclei bonded to each other, where spin information can be transmitted directly through the pair of bonding electrons. While nuclei polarize their electrons to the opposite spins, the bonding electron pair has opposite spins. Configurations with antiparallel nuclear spins are expected to be lower in energy. When coupling makes antiparallel states more favorable, J is considered to have a positive value. The one-bond coupling constant, 1J,...
1.1K
Spin–Spin Coupling: Three-Bond Coupling (Vicinal Coupling)01:22

Spin–Spin Coupling: Three-Bond Coupling (Vicinal Coupling)

1.1K
Vicinal or three-bond coupling is commonly observed between protons attached to adjacent carbons. Here, nuclear spin information is primarily transferred via electron spin interactions between adjacent C‑H bond orbitals. This generally favors the antiparallel arrangement of spins, so 3J values are usually positive.
The extent of coupling depends on the C‑C bond length, the two H‑C‑C angles, any electron-withdrawing substituents, and the dihedral angle between the...
1.1K
Singularity Functions for Shear01:26

Singularity Functions for Shear

193
In structural analysis, singularity functions are crucial in simplifying the representation of shear forces in beams under discontinuous loading. These functions describe discontinuous  variations in shear force across a beam with varying loads by using a single mathematical expression, regardless of the complexity of the loading conditions. The singularity functions are derived from creating a free-body diagram of the beam and then making conceptual cuts at specific points to examine the...
193
Radicals: Electronic Structure and Geometry01:07

Radicals: Electronic Structure and Geometry

4.2K
This lesson delves into the geometry of a radical, which is influenced by the electronic structure of the molecule. The principle is similar to that of a lone pair, where the unpaired electron influences the geometry at the radical center.
Accordingly, the structure of a trivalent radical lies between the geometries of carbocations and carbanions. An sp2-hybridized carbocation is trigonal planar, while an sp3-hybridized carbanion is trigonal pyramidal. Here, the difference in geometry is...
4.2K

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Video Experimental Relacionado

Updated: Sep 10, 2025

Spin Saturation Transfer Difference NMR SSTD NMR: A New Tool to Obtain Kinetic Parameters of Chemical Exchange Processes
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Spin Saturation Transfer Difference NMR SSTD NMR: A New Tool to Obtain Kinetic Parameters of Chemical Exchange Processes

Published on: November 12, 2016

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Regularización funcional de la densidad de espín para los dirradicales singlet

Yi Shi1, Yuming Shi2, Adam Wasserman3,4

  • 1State Key Laboratory for Artificial Microstructure and Mesoscopic Physics, Frontier Science Center for Nano-optoelectronics and School of Physics, Peking University, Beijing 100871, People's Republic of China.

Journal of chemical theory and computation
|August 22, 2025
PubMed
Resumen
Este resumen es generado por máquina.

Un nuevo enfoque de regularización funcional de densidad de espín (SR) corrige errores en los cálculos de la teoría funcional de densidad de simetría rota (DFT) para los diradicales singlet. Este método predice con precisión las barreras de energía para reacciones complejas, como la automatización del ciclobutadieno.

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Site Directed Spin Labeling and EPR Spectroscopic Studies of Pentameric Ligand-Gated Ion Channels
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Área de la Ciencia:

  • Química Cuántica
  • Química computacional
  • Química teórica

Sus antecedentes:

  • La teoría funcional de la densidad de simetría rota (DFT) se utiliza ampliamente para la correlación estática en los diradicales singlet.
  • Este método puede fallar para estructuras electrónicas complejas debido a la ruptura de simetría de espín artificial.
  • Los dirradicales singlet surgen de orbitales fronterizos (cuasi) degenerados.

Objetivo del estudio:

  • Desarrollar un método para corregir errores de ruptura de simetría artificial en DFT de simetría rota.
  • Mejorar la precisión de los cálculos de energía para sistemas con estructuras electrónicas complejas.

Principales métodos:

  • Introducción de un enfoque de regularización funcional de la densidad de espín (SR).
  • Integración de SR en el marco de la teoría funcional de la densidad de partición (PDFT).
  • Aplicación a la automatización del ciclobutadieno, un sistema con un estado de transición diradical singular.

Principales resultados:

  • El enfoque SR-PDFT corrige efectivamente los errores causados por la ruptura de simetría artificial.
  • Los cálculos DFT convencionales de simetría rota subestiman la energía del estado de transición de automatización para el ciclobutadieno.
  • El SR-PDFT produce alturas de barrera químicamente precisas para la reacción de automatización del ciclobutadieno.

Conclusiones:

  • El método SR-PDFT proporciona una forma robusta de manejar la correlación estática en los diradicals singlet.
  • Este enfoque supera las limitaciones de la DFT de simetría rota convencional para sistemas complejos.
  • Se logra una predicción precisa de las alturas de la barrera de reacción, lo que demuestra la eficacia del método.