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Network Covalent Solids02:18

Network Covalent Solids

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Network covalent solids contain a three-dimensional network of covalently bonded atoms as found in the crystal structures of nonmetals like diamond, graphite, silicon, and some covalent compounds, such as silicon dioxide (sand) and silicon carbide (carborundum, the abrasive on sandpaper). Many minerals have networks of covalent bonds.
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The structure of a crystalline solid, whether a metal or not, is best described by considering its simplest repeating unit, which is referred to as its unit cell. The unit cell consists of lattice points that represent the locations of atoms or ions. The entire structure then consists of this unit cell repeating in three dimensions. The three different types of unit cells present in the cubic lattice are illustrated in Figure 1.
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Cohesion is the attraction between molecules of the same type, such as water molecules. Water molecules have an overall neutral charge but are polar molecule. An oxygen atom in one water molecule has a partial negative charge that can bind to a hydrogen atom with a partial positive charge in a second water molecule, forming a hydrogen bond. Each water molecule can form up to four hydrogen bonds with other water molecules. Hydrogen bonds are responsible for water's cohesive nature.
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The VSEPR theory can be used to determine the electron pair geometries and molecular structures as follows:
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High-Density "Windowpane" Coordination Patterns of Water Clusters and Their NBO/NRT Characterization.

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  • 1Theoretical Chemistry Institute and Department of Chemistry, University of Wisconsin-Madison, Madison, WI 53706, USA.

Molecules (Basel, Switzerland)
|July 9, 2022
PubMed
Summary
This summary is machine-generated.

Proton-ordered water clusters form stable "windowpane" motifs with reduced bond angles, challenging traditional bonding models. This study reveals hydrogen bonding as resonance-covalent, unifying molecular and intermolecular interactions.

Keywords:
Grotthuss proton orderingglassy waterhydrogen bondingnatural bond orbitalsnatural bond ordersnatural resonance theoryquantum cluster equilibriumsupramolecular chemistrywater clusterswater wires

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Area of Science:

  • Physical Chemistry
  • Materials Science
  • Computational Chemistry

Background:

  • Cluster mixture models indicate higher coordination and density are needed for water clusters at high pressures.
  • Existing models often rely on tetrahedral hydrogen-bonding motifs.

Purpose of the Study:

  • To demonstrate the formation of proton-ordered water clusters with increased coordination and density.
  • To investigate novel cluster structures and their bonding characteristics.
  • To challenge dichotomous views of intermolecular vs. intramolecular bonding.

Main Methods:

  • Assembly of proton-ordered water clusters from cyclic tetramers or twisted bicyclic heptamers.
  • Formation of extended "Aufbau" sequences of two-, three-, and four-coordinate "windowpane" motifs.
  • Computation of free energy and natural resonance theory (NRT) bond orders.

Main Results:

  • Stable "windowpane" motifs with sharply reduced bond angles (~90°) were formed.
  • NRT bond orders quantitatively described cluster stability and linkage strengths.
  • NRT demonstrated consistency across supra-integer and sub-integer bond orders.

Conclusions:

  • Hydrogen bonding exemplifies resonance-covalent (fractional) bonding.
  • The study discounts the strict separation of electrostatics and covalency in bonding descriptions.
  • Novel water cluster structures provide insights into water behavior at high pressures.