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Periodic Classification of the Elements04:00

Periodic Classification of the Elements

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The periodic table arranges atoms based on increasing atomic number so that elements with the same chemical properties recur periodically. When their electron configurations are added to the table, a periodic recurrence of similar electron configurations in the outer shells of these elements is observed. Because they are in the outer shells of an atom, valence electrons play the most important role in chemical reactions. The outer electrons have the highest energy of the electrons in an atom...
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Valence Bond Theory and Hybridized Orbitals02:38

Valence Bond Theory and Hybridized Orbitals

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According to valence bond theory, a covalent bond results when: (1) an orbital on one atom overlaps an orbital on a second atom, and (2) the single electrons in each orbital combine to form an electron pair. The strength of a covalent bond depends on the extent of overlap of the orbitals involved. Maximum overlap is possible when the orbitals overlap on a direct line between the two nuclei.
A σ bond (single bond in a Lewis structure) is a covalent bond in which the electron density is...
27.7K
VSEPR Theory and the Basic Shapes02:52

VSEPR Theory and the Basic Shapes

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Overview of VSEPR Theory
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Electron Configurations02:46

Electron Configurations

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Electron configurations and orbital diagrams can be determined by applying the Aufbau principle (each added electron occupies the subshell of lowest energy available), Pauli exclusion principle (no two electrons can have the same set of four quantum numbers), and Hund’s rule of maximum multiplicity (whenever possible, electrons retain unpaired spins in degenerate orbitals).
The relative energies of the subshells determine the order in which atomic orbitals are filled (1s, 2s, 2p, 3s, 3p,...
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Crystal Field Theory - Tetrahedral and Square Planar Complexes02:46

Crystal Field Theory - Tetrahedral and Square Planar Complexes

48.1K
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,...
48.1K
VSEPR Theory02:37

VSEPR Theory

14.0K
Valence shell electron-pair repulsion theory (VSEPR theory) enables us to predict the molecular structure around a central atom from an examination of the number of bonds and lone electron pairs in its Lewis structure. The VSEPR model assumes that electron pairs in the valence shell of a central atom will adopt an arrangement that minimizes repulsions between these electron pairs by maximizing the distance between them. The electrons in the valence shell of a central atom form either bonding...
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Updated: Jan 15, 2026

Computation of Atmospheric Concentrations of Molecular Clusters from ab initio Thermochemistry
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Relativistic quintuple-zeta basis sets for the s block.

Marten L Reitsma1, Eifion H Prinsen1, Johan D Polet1

  • 1Van Swinderen Institute for Particle Physics and Gravity, University of Groningen, Nijenborgh 4, 9747 AG Groningen, The Netherlands.

The Journal of Chemical Physics
|October 10, 2025
PubMed
Summary

New relativistic basis sets of quintuple-zeta quality for s-block elements improve accuracy in heavy atom and molecule calculations. These advanced basis sets enable more precise computational chemistry, reducing uncertainty in scientific research.

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Area of Science:

  • Computational chemistry
  • Quantum chemistry
  • Relativistic quantum mechanics

Background:

  • Accurate calculations for heavy elements are crucial in chemistry and physics.
  • Existing basis sets may not fully capture relativistic effects and electron correlation for heavy systems.
  • The development of high-quality basis sets is essential for advancing computational modeling.

Purpose of the Study:

  • To present new relativistic basis sets of quintuple-zeta quality for s-block elements.
  • To optimize basis sets for accurate treatment of valence and core electrons, including diffuse functions.
  • To benchmark the performance of these basis sets for atomic and molecular properties.

Main Methods:

  • Development of relativistic basis sets with quintuple-zeta quality.
  • Optimization of self-consistent field exponents and correlating functions.
  • Utilizing multireference singles and doubles configuration interaction calculations.
  • Inclusion of diffuse functions for anions and related elements.

Main Results:

  • New quintuple-zeta relativistic basis sets were generated for s-block elements.
  • Basis sets showed smooth convergence towards the basis set limit with increasing quality.
  • Benchmarking demonstrated reliable performance for atomic and molecular properties.
  • The developed basis sets facilitate higher accuracy in heavy element calculations.

Conclusions:

  • The new quintuple-zeta basis sets represent a significant advancement for relativistic quantum chemistry.
  • These basis sets, combined with advanced computational methods, reduce uncertainty in calculations on heavy atoms and molecules.
  • The availability of these basis sets will aid researchers in achieving unprecedented accuracy in computational studies.