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Related Concept Videos

Hydrogen Bonds01:04

Hydrogen Bonds

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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...
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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....
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Hybridization of Atomic Orbitals II03:35

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sp3d and sp3d 2 Hybridization
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Hydrolysis of acid halides is a nucleophilic acyl substitution reaction in which acid halides react with water to give carboxylic acids. The reaction occurs readily and does not require acid or a base catalyst.
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Hybridization of Atomic Orbitals I03:24

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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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Radical Formation: Abstraction00:47

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The electron of an atom can be abstracted from a compound by a relatively unstable radical to generate a new radical of relatively greater stability. For example, an initiator which forms radicals by homolysis can abstract a suitable species like a hydrogen atom or a halogen atom from a compound to generate a new radical. This ability of radicals to propagate by abstraction is a crucial feature of radical chain reactions.
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Probing the Structure and Dynamics of Interfacial Water with Scanning Tunneling Microscopy and Spectroscopy
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Hydrogen-Atom Tunneling in Metaphosphorous Acid.

Weiyu Qian1, Xianxu Chu1, Chao Song1

  • 1College of Chemistry, Chemical Engineering and Materials Science, Soochow University, 215123, Suzhou, China.

Chemistry (Weinheim an Der Bergstrasse, Germany)
|April 18, 2020
PubMed
Summary

Metaphosphorous acid (HOPO) was generated and trapped in a nitrogen matrix. The anti-conformer of HOPO spontaneously rotates via hydrogen-atom tunneling, showing significant kinetic isotope effects.

Keywords:
IR spectroscopyconformationkinetic isotope effectsphosphorus acidsquantum mechanical tunneling

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Area of Science:

  • Physical Chemistry
  • Quantum Chemistry
  • Spectroscopy

Background:

  • Metaphosphorous acid (HOPO) is a crucial intermediate in phosphorus chemistry.
  • Understanding its conformational dynamics and reaction mechanisms is vital.

Purpose of the Study:

  • To generate and characterize syn- and anti-conformations of HOPO in the gas phase.
  • To investigate the rotamerization mechanism of the anti-conformer of HOPO.
  • To study kinetic isotope effects in the rotamerization process.

Main Methods:

  • High-vacuum flash pyrolysis (HVFP) of ethoxyphosphinidene oxide at ~1000 K to generate HOPO.
  • Trapping of HOPO in an N2 matrix at 2.8 K for spectroscopic analysis.
  • Analysis of spontaneous rotamerization and kinetic isotope effects (H/D, 16O/18O).

Main Results:

  • Syn- and anti-conformations of HOPO were successfully generated and trapped.
  • The anti-conformer of HOPO exhibited spontaneous rotamerization at 2.8 K.
  • Significant kinetic isotope effects were observed for H/D (>10^4 for DOPO) and 16O/18O (1.19 for H18OPO, 1.06 for HOP18O).

Conclusions:

  • Spontaneous rotamerization of anti-HOPO occurs via hydrogen-atom tunneling (HAT).
  • The observed kinetic isotope effects provide strong evidence for the HAT mechanism.
  • This study offers insights into the fundamental chemical dynamics of phosphorus compounds.