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Atomic Radii and Effective Nuclear Charge03:08

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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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Protons and neutrons, collectively called nucleons, are packed together tightly in a nucleus. With a radius of about 10−15 meters, a nucleus is quite small compared to the radius of the entire atom, which is about 10−10 meters. Nuclei are extremely dense compared to bulk matter, averaging 1.8 × 1014 grams per cubic centimeter. If the earth’s density were equal to the average nuclear density, the earth’s radius would be only about 200 meters.
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Coordination compounds and complexes exhibit different colors, geometries, and magnetic behavior, depending on the metal atom/ion and ligands from which they are composed. In an attempt to explain the bonding and structure of coordination complexes, Linus Pauling proposed the valence bond theory, or VBT, using the concepts of hybridization and the overlapping of the atomic orbitals. According to VBT, the central metal atom or ion (Lewis acid) hybridizes to provide empty orbitals of suitable...
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Does covalency increase or decrease across the actinide series? Implications for minor actinide partitioning.

Nikolas Kaltsoyannis1

  • 1Department of Chemistry, University College London, 20 Gordon Street, London WC1H 0AJ, UK.

Inorganic Chemistry
|June 7, 2012
PubMed
Summary

Quantum chemistry reveals complex bonding in actinides. Traditional methods may overestimate metal-ligand covalency, impacting nuclear waste separation strategies.

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Area of Science:

  • Inorganic Chemistry
  • Quantum Chemistry
  • Nuclear Chemistry

Background:

  • Covalent bonds typically involve atomic orbital overlap.
  • Actinide 5f orbitals exhibit unique behavior, influencing bonding characteristics.

Purpose of the Study:

  • To analyze metal-ligand covalency in actinide compounds (AnCp3 and AnCp4).
  • To compare traditional quantum-chemical tools with topological electron density analysis.

Main Methods:

  • Quantum-chemical calculations for actinide complexes.
  • Population analysis and spin density calculations.
  • Topological analysis using the Quantum Theory of Atoms in Molecules (QTAIM).

Main Results:

  • Traditional methods predict significant covalency due to orbital mixing, despite minimal atomic orbital overlap.
  • QTAIM analysis provides a different perspective on metal-ligand bonding.
  • Discrepancies highlight challenges in assessing covalency for actinides.

Conclusions:

  • Care is needed when using quantum chemistry to assess actinide-ligand covalency.
  • Findings have implications for minor actinide partitioning in nuclear waste management.
  • Understanding bonding is crucial for designing effective actinide extractants.