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Spin–Spin Coupling Constant: Overview01:08

Spin–Spin Coupling Constant: Overview

1.1K
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...
1.1K
Spin–Spin Coupling: Two-Bond Coupling (Geminal Coupling)01:20

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

1.2K
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...
1.2K
Olefin Metathesis Polymerization: Ring-Opening Metathesis Polymerization (ROMP)01:16

Olefin Metathesis Polymerization: Ring-Opening Metathesis Polymerization (ROMP)

2.8K
Ring-opening metathesis polymerization or ROMP involves strained cycloalkenes as starting materials. The mechanism of ROMP proceeds by reacting cycloalkene with Grubbs catalyst to give metallacyclobutane intermediate which undergoes a ring-opening reaction to form new carbene. The new carbene reacts with another molecule of cycloalkene. Repetition of these steps leads to the formation of an unsaturated open-chain polymer product. All these steps are reversible, however, relieving the ring...
2.8K
¹H NMR of Conformationally Flexible Molecules: Variable-Temperature NMR01:15

¹H NMR of Conformationally Flexible Molecules: Variable-Temperature NMR

1.3K
The axial and equatorial protons in cyclohexane can be distinguished by performing a variable-temperature NMR experiment. In this process, except for one proton, the remaining eleven protons are replaced by deuterium. The deuterium substitution avoids the possible peak splitting caused by the spin-spin coupling between the adjacent protons. The remaining proton flips between the axial and equatorial positions.
1.3K
¹H NMR of Conformationally Flexible Molecules: Temporal Resolution00:52

¹H NMR of Conformationally Flexible Molecules: Temporal Resolution

969
At room temperature, the chair conformer of cyclohexane undergoes rapid ring flipping between two equivalent chair conformers at a rate of approximately 105 times per second. These two chair conformers are in equilibrium. The rapid ring flipping results in the interconversion of the axial proton to an equatorial proton and an equatorial to the axial proton. Such interconversions are too rapid and cannot be detected on the NMR timescale. Hence, the NMR spectrometer cannot distinguish between the...
969
Spin–Spin Coupling: Three-Bond Coupling (Vicinal Coupling)01:22

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

1.2K
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...
1.2K

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Related Experiment Video

Updated: Oct 29, 2025

Exploring Caspase Mutations and Post-Translational Modification by Molecular Modeling Approaches
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Exploring Caspase Mutations and Post-Translational Modification by Molecular Modeling Approaches

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Non-adiabatic ring polymer molecular dynamics with spin mapping variables.

Duncan Bossion1, Sutirtha N Chowdhury1, Pengfei Huo1

  • 1Department of Chemistry, University of Rochester, 120 Trustee Road, Rochester, New York 14627, USA.

The Journal of Chemical Physics
|July 9, 2021
PubMed
Summary
This summary is machine-generated.

We introduce a new spin mapping non-adiabatic ring polymer molecular dynamics (SM-NRPMD) method. This approach accurately simulates quantum dynamics, offering advantages over existing methods for thermal equilibrium systems.

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Area of Science:

  • Quantum Chemistry
  • Molecular Dynamics
  • Computational Physics

Background:

  • Simulating quantum dynamics in complex molecular systems is computationally challenging.
  • Existing methods often struggle with accurate sampling of quantum statistics and computational efficiency.

Purpose of the Study:

  • To develop a novel, efficient, and accurate method for simulating non-adiabatic quantum dynamics.
  • To introduce the spin mapping non-adiabatic ring polymer molecular dynamics (SM-NRPMD) approach.

Main Methods:

  • Derivation of the path-integral partition function using spin coherent states and ring polymer formalism.
  • Justification of a Hamiltonian for coupled spin mapping variables and nuclear ring polymer dynamics.
  • Numerical validation using nuclear position and population auto-correlation functions.

Main Results:

  • The SM-NRPMD method shows excellent agreement with numerically exact results for non-adiabatic model systems.
  • Spin mapping variables provide nearly time-independent expectation values for equilibrium systems.
  • SM-NRPMD demonstrates invariant dynamics under potential partitioning variations.

Conclusions:

  • The SM-NRPMD method is a highly accurate and efficient tool for quantum dynamics simulations.
  • It offers significant advantages over harmonic oscillator mapping for systems in thermal equilibrium.
  • The method's robustness is confirmed by its invariance to potential partitioning schemes.