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Related Concept Videos

Crystal Field Theory - Tetrahedral and Square Planar Complexes02:46

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Tetrahedral Complexes
Crystal field theory (CFT) is applicable to molecules in geometries other than octahedral. In octahedral complexes, the lobes of the dx2−y2 and dz2 orbitals point directly at the ligands. For tetrahedral complexes, the d orbitals remain in place, but with only four ligands located between the axes. None of the orbitals points directly at the tetrahedral ligands. However, the dx2−y2 and dz2 orbitals (along the Cartesian axes) overlap with the ligands less than the dxy,...
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Sigmatropic rearrangements are a class of pericyclic reactions in which a σ bond migrates from one part of a π system to another. These are intramolecular rearrangements where the total number of σ and π bonds remain unchanged.
Sigmatropic shifts are classified based on an order term [i, j ], where i and j indicate the number of atoms across which each end of the σ bond migrates. Below are examples of a [3,3] sigmatropic shift in 1,5-hexadiene, referred...
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Properties of Transition Metals

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Transition metals are defined as those elements that have partially filled d orbitals. As shown in Figure 1, the d-block elements in groups 3–12 are transition elements. The f-block elements, also called inner transition metals (the lanthanides and actinides), also meet this criterion because the d orbital is partially occupied before the f orbitals.
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Electrocyclic reactions are reversible reactions. They involve an intramolecular cyclization or ring-opening of a conjugated polyene. Shown below are two examples of electrocyclic reactions. In the first reaction, the formation of the cyclic product is favored. In contrast, in the second reaction, ring-opening is favored due to the high ring strain associated with cyclobutene formation.
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Crystal Field Theory
To explain the observed behavior of transition metal complexes (such as colors), a model involving electrostatic interactions between the electrons from the ligands and the electrons in the unhybridized d orbitals of the central metal atom has been developed. This electrostatic model is crystal field theory (CFT). It helps to understand, interpret, and predict the colors, magnetic behavior, and some structures of coordination compounds of transition metals.
CFT focuses on...
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Phase Diagram01:19

Phase Diagram

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The phase of a given substance depends on the pressure and temperature. Thus, plots of pressure versus temperature showing the phase in each region provide considerable insights into the thermal properties of substances. Such plots are known as phase diagrams. For instance, in the phase diagram for water (Figure 1), the solid curve boundaries between the phases indicate phase transitions (i.e., temperatures and pressures at which the phases coexist).
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Synthesis of Non-uniformly Pr-doped SrTiO3 Ceramics and Their Thermoelectric Properties
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Phase transformations among TiO2 polymorphs.

Miao Song1, Zexi Lu, Dongsheng Li

  • 1Physical and Computational Sciences Directorate, Pacific Northwest National Laboratory, Richland, WA 99352, USA. Dongsheng.Li2@pnnl.gov.

Nanoscale
|November 17, 2020
PubMed
Summary
This summary is machine-generated.

Researchers observed atomic-scale transformations between titanium dioxide (TiO2) polymorphs using advanced microscopy and theory. New transformation pathways were discovered, revealing insights into material property control and electron-beam effects.

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Area of Science:

  • Materials Science
  • Solid-State Chemistry
  • Nanotechnology

Background:

  • Polymorphs are crucial for material properties, but their transformation mechanisms lack atomic-scale understanding.
  • Direct observation of structural evolution during phase transitions is limited.
  • Titanium dioxide (TiO2) exhibits diverse polymorphs (anatase, rutile, brookite) with distinct properties.

Purpose of the Study:

  • To investigate the atomic-scale structural evolution during phase transformations of TiO2 polymorphs.
  • To identify novel transformation pathways between TiO2 polymorphs.
  • To elucidate the role of electron-beam irradiation on TiO2 phase stability and transformation.

Main Methods:

  • In situ transmission electron microscopy (TEM) for real-time atomic observation.
  • Density functional theory (DFT) calculations for mechanistic insights and energy barrier analysis.
  • Controlled electron-beam irradiation experiments at varying temperatures.

Main Results:

  • Observed atomic structural evolutions for anatase to rutile, brookite, R-phase, and TiO transformations.
  • Discovered new transformation pathways, including specific crystallographic orientations ([001]A||[100]R, (020)A||(01[combining macron]1)R and [001]A||[001]B, (020)A||(220)B).
  • Quantified Ti-O bond breaking/reforming (over 16%) with energy barriers of 0.7-1.0 eV/TiO2.
  • Revealed anisotropic electron-beam effects dependent on crystallographic orientation, inducing transformations to TiO2-R or TiO.

Conclusions:

  • Atomic-scale understanding of TiO2 polymorph transformations is achievable through integrated experimental and computational methods.
  • New transformation pathways and anisotropic electron-beam effects were identified, advancing knowledge of TiO2 behavior.
  • Findings provide guidance for controlling TiO2 polymorphs and interpreting in situ TEM studies for materials design.