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Crystal Field Theory
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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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Electron Counting and High-Pressure Phase Transformations in Metal Hexaborides.

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Electron counting rules accurately predict pressure-induced structural changes in alkaline earth hexaborides. Density functional theory (DFT) calculations reveal unique bonding in barium hexaboride under pressure.

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Area of Science:

  • Materials Science
  • Solid-State Chemistry
  • Computational Materials Science

Background:

  • Alkaline earth hexaborides (AEB6) exhibit complex structural behaviors under pressure.
  • Understanding pressure-induced transitions is crucial for materials design.

Purpose of the Study:

  • To theoretically investigate pressure-induced structural transitions in CaB6, SrB6, and BaB6.
  • To assess the applicability of electron counting rules to solid-state metal borides under pressure.
  • To elucidate the bonding mechanisms responsible for structural anomalies.

Main Methods:

  • Density Functional Theory (DFT) calculations.
  • Application and validation of gas-phase borane electron counting rules.

Main Results:

  • Electron counting rules successfully predict most structural phases of AEB6 under pressure.
  • A unique intermediate-pressure phase in BaB6 deviates from electron counting rules.
  • DFT reveals significant B-Ba covalency and B-B pi bonding in the anomalous BaB6 phase.

Conclusions:

  • Electron counting rules are valuable for predicting solid-state structures under pressure.
  • DFT provides insights into bonding anomalies, aiding materials discovery.
  • Understanding structure-bonding relationships can guide the design of novel boride materials.