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Thermodynamic potentials are state functions that are extremely useful in analyzing a thermodynamic system. They have dimensions of energy. The four important thermodynamic potentials are internal energy, enthalpy, Helmholtz free energy, and Gibbs free energy. These thermodynamic potentials can be expressed using two of the following variables: pressure, volume, temperature, and entropy. These two variables are expressed as the rate of change of the thermodynamic potential with respect to other...
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Schottky defects arise when some lattice points in a crystal, such as those in NaCl, remain unoccupied, creating lattice vacancies without disturbing the overall electrical neutrality of the crystal. This defect is common in ionic crystals where the positive and negative ions are similar in size, as seen in sodium chloride and cesium chloride. The presence of Schottky defects enables the crystal to conduct electricity to a small extent through an ionic mechanism. Electric fields cause nearby...
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Computation of Atmospheric Concentrations of Molecular Clusters from ab initio Thermochemistry
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Delocalization errors in density functionals and implications for main-group thermochemistry.

Erin R Johnson1, Paula Mori-Sánchez, Aron J Cohen

  • 1Department of Chemistry, Duke University, Durham, North Carolina 27708, USA.

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Approximate density functionals struggle with Diels-Alder reactions and aluminum dimerization energetics. Delocalization error explains why cyclic products are often underbound, guiding the selection of better computational chemistry tools.

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Area of Science:

  • Computational chemistry
  • Quantum chemistry
  • Theoretical chemistry

Background:

  • Approximate density functionals (DFs) are widely used in computational chemistry.
  • Certain reaction classes, like Diels-Alder and aluminum complex dimerization, present challenges for these DFs.
  • These reactions often involve the formation of cyclic or bicyclic structures.

Purpose of the Study:

  • To analyze the difficulties of approximate DFs in describing the energetics of Diels-Alder reactions and aluminum complex dimerization.
  • To provide a consistent interpretation of these energetic errors using the concept of delocalization error.
  • To offer guidance on selecting appropriate DFs for specific chemical reactions.

Main Methods:

  • Analysis of the performance of various approximate density functionals.
  • Focus on reaction classes forming cyclic or bicyclic products.
  • Interpretation of results through the lens of delocalization error.

Main Results:

  • Most approximate DFs considered underbind the cyclic and bicyclic products of Diels-Alder and aluminum dimerization reactions.
  • Delocalization error in DFs leads to inaccurate energetics, particularly for localized electronic densities found in these products.
  • A correlation is established between delocalization error and errors in main-group thermochemistry.

Conclusions:

  • Delocalization error is a key factor explaining the underbinding of cyclic products by approximate DFs.
  • Functionals with minimal delocalization error are recommended for reactions involving loss of conjugation or formation of complex molecular architectures.
  • This understanding improves the reliability of theoretical studies in computational chemistry.