Sigma and Pi Bonds for Diatomic Oxygen Molecule

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SUMMARY

The discussion centers on the molecular orbital theory of diatomic oxygen, which indicates that it has σ2px, π2py, and π2pz orbitals filled with two unpaired electrons in antibonding states. This results in a bond order of 2, contrasting with the valence bond theory that suggests a double bond configuration. The presence of unpaired electrons in antibonding orbitals explains the paramagnetic properties of oxygen, challenging the accuracy of the valence bond theory. Historical references to research by Wheland and Lennard-Jones from 1937 support these conclusions.

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  • Molecular orbital theory fundamentals
  • Understanding of bond order calculations
  • Knowledge of paramagnetism in diatomic molecules
  • Familiarity with valence bond theory
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  • Study the implications of antibonding orbitals in molecular stability
  • Explore the differences between molecular orbital theory and valence bond theory
  • Investigate the historical context of molecular orbital theory development
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Chemistry students, molecular physicists, and educators seeking a deeper understanding of the bonding characteristics and properties of diatomic oxygen.

Conservation
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According to the Molecular orbital theory, diatomic oxygen should have σ2px (internuclear axis) and \pi2py and \pi2pz orbitals filled with two unpaired electrons, one at antibonding \pi2py and the other at antibonding \pi2pz. And of course, the 2s bonding and antibonding orbitals as well.
According to the molecular orbital theory, does this imply that diatomic oxygen possesses three "bonds" and one set of unpaired electrons, opposed to the double bond (sigma pi) implied by the valence bond theory?

Thank you.
 
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The unpaired electrons are in fact antibonding, so that the bond order is 3-2x1/2=2.
In contrast to folk expositions of VB theory, VB theory predicts the same ground state as MO theory and not two double bonds, which rather describes bonding in the excited singulet oxygen.
This was shown already in 1937 by Wheland and Lennard-Jones:
http://pubs.rsc.org/en/content/articlelanding/1937/tf/tf9373301499#!divAbstract
 
Right, hence the paramagnetic properties displayed in oxygen to point out the flaws of VB theory.

However, if the two unpaired electrons are antibonding, does that make the π2py and π2pz bonds "half" bonds? So one "full" sigma bonds at x and two "half" bonds at y and z planes to add up to two?
 
Conservation said:
Right, hence the paramagnetic properties displayed in oxygen to point out the flaws of VB theory.

As I tried to explain, VB gives a correct description of bonding in oxygen, so it is not flawed.
Furthermore, also the singlet state of oxygen is about as paramagnetic as the triplet state, due to orbital momentum, so oxygen being paramagnetic does not help to decide whether the ground state is singlet or triplet.

However, if the two unpaired electrons are antibonding, does that make the π2py and π2pz bonds "half" bonds? So one "full" sigma bonds at x and two "half" bonds at y and z planes to add up to two?
Yes, the pi bonds both have a bond order of 1/2.
 

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