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Related Concept Videos

Woodward–Hoffmann Selection Rules and Microscopic Reversibility01:34

Woodward–Hoffmann Selection Rules and Microscopic Reversibility

Electrocyclic reactions, cycloadditions, and sigmatropic rearrangements are concerted pericyclic reactions that proceed via a cyclic transition state. These reactions are stereospecific and regioselective. The stereochemistry of the products depends on the symmetry characteristics of the interacting orbitals and the reaction conditions. Accordingly, pericyclic reactions are classified as either symmetry-allowed or symmetry-forbidden. Woodward and Hoffmann presented the selection criteria for...
UV–Vis Spectroscopy: Woodward–Fieser Rules01:29

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UV–Visible absorption spectra of conjugated dienes arise from the lowest energy π → π* transitions. The light-absorbing part of the molecule is called the chromophore, and the substituents directly attached to the chromophore are called auxochromes. A strong correlation exists between the absorption maxima, λmax, and the structure of a conjugated π system. The Woodward–Fieser rules predict the value of λmax for a given structure by adding the contributions...
Molecular Orbital Theory I02:35

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Valence Bond Theory and Hybridized Orbitals02:38

Valence Bond Theory and Hybridized Orbitals

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...
Molecular Orbital Theory II03:51

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Hückel's Rule Diagram of π MOs: Frost Circle01:08

Hückel's Rule Diagram of π MOs: Frost Circle

The Frost circle or the inscribed polygon method is a graphical method for determining the relative energies of π molecular orbitals (MOs) for planar, fully conjugated, and monocyclic compounds. This method was first described by A. A. Frost and Boris Musulin in 1953.
A Frost circle is constructed by drawing a polygon whose number of edges is equal to the number of carbons of the given cyclic system, with one of the vertices pointing down. Then, a circle is drawn enclosing the polygon so that...

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Excitonic Hamiltonians for Calculating Optical Absorption Spectra and Optoelectronic Properties of Molecular Aggregates and Solids
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The Woodward-Hoffmann rules reinterpreted by conceptual density functional theory.

Paul Geerlings1, Paul W Ayers, Alejandro Toro-Labbé

  • 1Eenheid Algemene Chemie (ALGC), Vrije Universiteit Brussel (VUB), Pleinlaan 2, 1050, Brussels, Belgium. pgeerlin@vub.ac.be

Accounts of Chemical Research
|January 31, 2012
PubMed
Summary

This study reinterprets Woodward-Hoffmann rules for pericyclic reactions using conceptual density functional theory (DFT). New methods based on electron density offer insights into chemical reactivity, complementing traditional quantum mechanics approaches.

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Area of Science:

  • Chemical Physics
  • Quantum Chemistry
  • Theoretical Chemistry

Background:

  • Quantum mechanics (QM) and density functional theory (DFT) are crucial for understanding chemical reactivity.
  • Woodward-Hoffmann (WH) rules predict pericyclic reaction outcomes using orbital symmetry.
  • Conceptual DFT offers precise chemical concepts and reactivity insights.

Purpose of the Study:

  • To develop a conceptual DFT approach for pericyclic reactions.
  • To reinterpret WH rules using density-only methods.
  • To link local electron density descriptors with global hardness response.

Main Methods:

  • Utilizing the dual descriptor f((2))(r) (a density response function).
  • Analyzing the evolution of chemical hardness at the reaction's onset.
  • Applying simple quantum chemical calculations on model reaction coordinates.

Main Results:

  • The dual descriptor provides pictorial representations similar to WH orbital symmetry.
  • Chemical hardness evolution connects to Zimmerman's alternative WH rule approach.
  • A relationship was found between the local dual descriptor and global hardness response.

Conclusions:

  • Conceptual DFT successfully reinterprets WH rules for pericyclic reactions.
  • Electron density is fundamental for chemical information, as shown by DFT.
  • Density-only approaches offer a powerful alternative for understanding chemical reactivity.