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Electrophilic Addition to Alkynes: Halogenation02:38

Electrophilic Addition to Alkynes: Halogenation

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Introduction
Halogenation is another class of electrophilic addition reactions where a halogen molecule gets added across a π bond. In alkynes, the presence of two π bonds allows for the addition of two equivalents of halogens (bromine or chlorine). The addition of the first halogen molecule forms a trans-dihaloalkene as the major product and the cis isomer as the minor product. Subsequent addition of the second equivalent yields the tetrahalide.
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The chair conformation is the most stable form of cyclohexane due to the absence of angle and torsional strain. The absence of angle strain is a result of cyclohexane’s bond angle being very close to the ideal tetrahedral bond angle of 109.5° in its chair conformer. Similarly, the torsional strain is also absent owing to the perfectly staggered arrangement of bonds.
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Thermal cycloadditions are reactions where the source of activation energy needed to initiate the reaction is provided in the form of heat. A typical example of a thermally-allowed cycloaddition is the Diels–Alder reaction, which is a [4 + 2] cycloaddition. In contrast, a [2 + 2] cycloaddition is thermally forbidden.
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Conformations of Cyclohexane02:11

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Cyclohexane does not exist in a planar form due to the high angle and torsional strain it would experience in the planar structure. Instead, it adopts non-planar chair and boat conformations.
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Metallic Solids02:37

Metallic Solids

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Metallic solids such as crystals of copper, aluminum, and iron are formed by metal atoms. The structure of metallic crystals is often described as a uniform distribution of atomic nuclei within a “sea” of delocalized electrons. The atoms within such a metallic solid are held together by a unique force known as metallic bonding that gives rise to many useful and varied bulk properties.
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Cycloheptatriene is a neutral monocyclic unsaturated hydrocarbon that consists of an odd number of carbon atoms and an intervening sp3 carbon in the ring. The three double bonds in the ring correspond to 6 π electrons, which is a Huckel number, and therefore satisfies the criteria of 4n + 2 π electrons. However, the intervening sp3 carbon disrupts the continuous overlap of p orbitals. As a result, cycloheptatriene is not aromatic.
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Cyclic Single Atom Vertical Manipulation on a Nonmetallic Surface.

David Abbasi-Pérez1, Hongqian Sang1,2, Filipe L Q Junqueira3

  • 1Department of Physics, King's College London, London WC2R 2LS, U.K.

The Journal of Physical Chemistry Letters
|November 16, 2021
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Summary
This summary is machine-generated.

Researchers developed a computational method for controlled single-atom manipulation on surfaces. Specific atomic force microscope tips can repeatedly pick up and deposit atoms like Gallium and Arsenic on GaAs(110).

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Area of Science:

  • Surface Science
  • Atomic Manipulation
  • Computational Materials Science

Background:

  • Controlled manipulation of single atoms on surfaces is crucial for developing advanced materials and nanoscale devices.
  • Existing experimental techniques face challenges in achieving reliable and repeatable atomic manipulation.

Purpose of the Study:

  • To computationally explore cyclical vertical manipulation of single atoms on the Gallium Arsenide (GaAs)(110) surface.
  • To identify suitable atomic force microscope (AFM) tip configurations for repeatable atom manipulation.

Main Methods:

  • Utilized first-principles simulations to model AFM tip-sample interactions.
  • Investigated GaAs and Gold (Au)-terminated AFM tips with varied crystalline terminations.
  • Simulated tip-sample interactions for picking up and depositing adatoms (Ga, As, Al, Au).

Main Results:

  • Identified specific AFM tip apexes capable of repeatedly picking up and depositing adatoms (Ga, As, Al, Au) on GaAs(110).
  • Discovered a modify-restore cycle that resets the AFM tip apex after each manipulation.
  • Determined specific lateral and vertical tip-sample distance windows for successful atom extraction and deposition, varying per atom.

Conclusions:

  • A computational strategy successfully identified conditions for cyclical single-atom manipulation on GaAs(110).
  • The findings propose a practical experimental protocol for cyclical manipulation of single atoms on nonmetallic surfaces.
  • This work paves the way for precise atomic assembly using AFM techniques.