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Related Concept Videos

Hydrogen Bonds01:04

Hydrogen Bonds

A hydrogen bond is formed when a weakly positive hydrogen atom already bonded to one electronegative atom (for example, the oxygen in the water molecule) is attracted to another electronegative atom from another polar molecule, such as water (H2O), hydrogen fluoride (HF), or ammonia (NH3). The huge electronegativity difference between the H atom (2.1) and the atom to which it is bonded (4.0 for an F atom, 3.5 for an O atom, or 3.0 for an N atom), combined with the very small size of an H atom...
Hydrogen Bonds00:26

Hydrogen Bonds

Hydrogen bonds are weak attractions between atoms that have formed other chemical bonds. One of these atoms is electronegative, like oxygen, and has a partial negative charge. The other is a hydrogen atom that has bonded with another electronegative atom and has a partial positive charge.
Hydrogen Bonds Control the World!
Because hydrogen has very weak electronegativity when it binds with a strongly electronegative atom, such as oxygen or nitrogen, electrons in the bond are unequally shared.
Spin–Spin Coupling: One-Bond Coupling01:17

Spin–Spin Coupling: One-Bond Coupling

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

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

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...
Imperfections in Crystal Structure: Stoichiometric Point Defects01:26

Imperfections in Crystal Structure: Stoichiometric Point Defects

Schottky defects arise when some lattice points in a crystal, such as those in NaCl, remain unoccupied, creating lattice vacancies without disturbing the overall electrical neutrality of the crystal. This defect is common in ionic crystals where the positive and negative ions are similar in size, as seen in sodium chloride and cesium chloride. The presence of Schottky defects enables the crystal to conduct electricity to a small extent through an ionic mechanism. Electric fields cause nearby...
Hybridization of Atomic Orbitals I03:24

Hybridization of Atomic Orbitals I

The mathematical expression known as the wave function, ψ, contains information about each orbital and the wavelike properties of electrons in an isolated atom. When atoms are bound together in a molecule, the wave functions combine to produce new mathematical descriptions that have different shapes. This process of combining the wave functions for atomic orbitals is called hybridization and is mathematically accomplished by the linear combination of atomic orbitals. The new orbitals that...

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A hydrogen-bond flip-flop through a Bjerrum-type defect.

Martin Olschewski1, Jörg Lindner, Peter Vöhringer

  • 1Institut für Physikalische und Theoretische Chemie, Rheinische Friedrich-Wilhelms-Universität, Wegelerstrasse 12, 53115 Bonn, Germany.

Angewandte Chemie (International Ed. in English)
|February 19, 2013
PubMed
Summary

The reversal of intramolecular hydrogen bonds was studied using femtosecond two-dimensional infrared exchange spectroscopy. This flip-flop motion occurs via concerted torsional isomerizations on a picosecond timescale.

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Area of Science:

  • Chemical Physics
  • Molecular Dynamics
  • Spectroscopy

Background:

  • Intramolecular hydrogen bonds play crucial roles in molecular structure and function.
  • Understanding the dynamics of hydrogen bond rearrangement is essential for various chemical and biological processes.

Purpose of the Study:

  • To investigate the dynamic mechanism of intramolecular hydrogen bond reversal.
  • To determine the timescale and pathways involved in H-bond dynamics.

Main Methods:

  • Utilized femtosecond two-dimensional infrared (2D IR) exchange spectroscopy.
  • Applied advanced spectroscopic techniques to probe ultrafast molecular motions.

Main Results:

  • Observed a flip-flop motion corresponding to intramolecular hydrogen bond reversal.
  • Identified two concerted disrotatory torsional isomerizations as the facilitating mechanism.
  • Determined the H-bond reversal occurs on a timescale of approximately 2 picoseconds.

Conclusions:

  • The study elucidates the ultrafast dynamics of intramolecular hydrogen bond reversal.
  • Provides insights into the concerted nature of torsional isomerizations in H-bond dynamics.
  • Highlights the utility of 2D IR exchange spectroscopy for studying rapid molecular events.