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Spin–Spin Coupling: Three-Bond Coupling (Vicinal Coupling)01:22

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

1.3K
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 involved orbitals. The...
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Spin–Spin Coupling: One-Bond Coupling01:17

Spin–Spin Coupling: One-Bond Coupling

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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,...
1.2K
Spin–Spin Coupling: Two-Bond Coupling (Geminal Coupling)01:20

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

1.3K
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...
1.3K
Van der Waals Equation01:10

Van der Waals Equation

5.2K
The ideal gas law is an approximation that works well at high temperatures and low pressures. The van der Waals equation of state (named after the Dutch physicist Johannes van der Waals, 1837−1923) improves it by considering two factors.
First, the attractive forces between molecules, which are stronger at higher densities and reduce the pressure, are considered by adding to the pressure a term equal to the square of the molar density multiplied by a positive coefficient a. Second, the volume...
5.2K
Free Energy Changes for Nonstandard States03:25

Free Energy Changes for Nonstandard States

12.8K
The free energy change for a process taking place with reactants and products present under nonstandard conditions (pressures other than 1 bar; concentrations other than 1 M) is related to the standard free energy change according to this equation:
12.8K
¹H NMR: Long-Range Coupling01:27

¹H NMR: Long-Range Coupling

2.3K
The coupling interactions of nuclei across four or more bonds are usually weak, with J values less than 1 Hz. While these are usually not observed in spectra, the presence of multiple bonds along the coupling pathway can result in observable long-range coupling.
In alkenes, spin information is communicated via σ–π overlap, as seen in allylic (four-bond) and homoallylic (five-bond) couplings. These coupling interactions are stronger when the σ bond is parallel to the alkene...
2.3K

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Related Experiment Video

Updated: Nov 22, 2025

Excitonic Hamiltonians for Calculating Optical Absorption Spectra and Optoelectronic Properties of Molecular Aggregates and Solids
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Excitonic Hamiltonians for Calculating Optical Absorption Spectra and Optoelectronic Properties of Molecular Aggregates and Solids

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Nonadiabatic couplings from a variational excited state method based on constrained DFT.

Pablo Ramos1, Michele Pavanello1

  • 1Department of Chemistry, Rutgers University, Newark, New Jersey 07102, USA.

The Journal of Chemical Physics
|January 8, 2021
PubMed
Summary
This summary is machine-generated.

Excited Constrained Density Functional Theory (XCDFT) now computes nonadiabatic coupling vectors (NACVs) for excited states. This advancement enables more accurate simulations of chemical dynamics for excited molecules.

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Area of Science:

  • Computational Chemistry
  • Quantum Chemistry
  • Theoretical Chemistry

Background:

  • Density Functional Theory (DFT) is a powerful tool for ground state electronic structure calculations.
  • Extending DFT to excited states is crucial for understanding photochemistry and photophysics.
  • Existing methods for excited states often face computational challenges and limitations.

Purpose of the Study:

  • To develop and implement a method for calculating nonadiabatic coupling vectors (NACVs) for excited states using Excited Constrained DFT (XCDFT).
  • To assess the accuracy and viability of XCDFT for simulating nonadiabatic dynamics.

Main Methods:

  • Utilized Excited Constrained Density Functional Theory (XCDFT), a variational method extending ground state DFT.
  • Developed an analytical approach for computing NACVs using density functional perturbation theory.
  • Applied the method to pilot calculations for systems including H3, selenoacrolein, and azobenzene.

Main Results:

  • Successfully computed NACVs between the first excited state (XCDFT) and the ground state.
  • XCDFT energy surfaces and NACVs showed good agreement with benchmark values, respecting sum rules.
  • Demonstrated the method's applicability despite challenges like wavefunction nonorthogonality.

Conclusions:

  • XCDFT is a viable and accurate method for calculating NACVs for excited states.
  • The developed methodology supports the use of XCDFT in nonadiabatic dynamics simulations.
  • This work advances the capability of DFT for studying excited-state phenomena.