Sigma and Pi Bonds for Diatomic Oxygen Molecule

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Discussion Overview

The discussion centers on the bonding characteristics of the diatomic oxygen molecule as analyzed through Molecular Orbital (MO) theory and Valence Bond (VB) theory. Participants explore the implications of unpaired electrons in antibonding orbitals and how these relate to bond order and the nature of bonding in oxygen.

Discussion Character

  • Technical explanation
  • Debate/contested
  • Conceptual clarification

Main Points Raised

  • One participant asserts that according to MO theory, diatomic oxygen has σ2px, π2py, and π2pz orbitals filled with unpaired electrons in antibonding states, suggesting a bond order of 3-2x1/2=2.
  • Another participant challenges the notion that VB theory is flawed, arguing that it predicts the same ground state as MO theory and does not imply two double bonds.
  • There is a question raised about whether the antibonding nature of the unpaired electrons implies that the π2py and π2pz bonds can be considered "half" bonds, leading to a total bond order of two when combined with the full sigma bond.
  • One participant agrees that the π bonds have a bond order of 1/2, supporting the idea of "half" bonds.

Areas of Agreement / Disagreement

Participants express differing views on the validity of VB theory in explaining the bonding in oxygen, with some arguing for its correctness while others highlight its limitations. The discussion remains unresolved regarding the interpretation of bond order and the nature of the bonds in diatomic oxygen.

Contextual Notes

There are unresolved aspects regarding the definitions of bond order and the implications of unpaired electrons in antibonding orbitals. The discussion also touches on the relationship between paramagnetism and the ground state of oxygen, which remains a point of contention.

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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