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In a paper by Peng et. al.,[1] I read about the valence band maximum of $\ce{TiO2}$ consists of non-bonding O pπ orbitals

... the valence band maximum (VBM) consists of non-bonding O pπ states

What does non-bonding pπ orbital mean? If there is not a chemical bond, why did they call it a π orbital?

References:

  1. Peng, H.; Li, J.; Li, S.; Xia, J. First-principles study of the electronic structures and magnetic properties of 3d transition metal-doped anatase TiO2. J. Phys.: Condens. Matter 2008, 20 (12), 125207. DOI: 10.1088/0953-8984/20/12/125207.
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  • $\begingroup$ Besides the fact that orbital as functions do exist independently of their occupancy, the fact that those orbitals are involved in the valence band formation means that are occupied. $\endgroup$
    – Alchimista
    Commented Sep 9, 2021 at 10:34
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    $\begingroup$ Well, you have that planar triangle around O, and a $p$ orbital perpendicular to it, so it feels kinda natural to call that orbital $\pi$. $\endgroup$ Commented Sep 9, 2021 at 10:34
  • $\begingroup$ And, if you are concerned by non bonding orbitals in general, then Wikipedia can be a starting point en.m.wikipedia.org/wiki/Non-bonding_orbital $\endgroup$
    – Alchimista
    Commented Sep 9, 2021 at 10:37
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    $\begingroup$ $\pi$ is a symmetry label, not a label that indicates whether there is a bond or not. These concepts are orthogonal to one another. $\endgroup$ Commented Sep 9, 2021 at 11:40

1 Answer 1

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When you have atoms bonded all in one plane, there will be $p$ orbitals oriented perpendicular to the plane which may not interact significantly with adjacent atoms. Such orbitals would then be called nonbonding.

We may compare water with carbon dioxide. Introductory textbooks often describe the oxygen in water as having a distorted $sp^3$ hybridization, but in reality only two oxygen $p$ orbitals mix with the hydrogen and oxygen $s$ orbitals to form the bonds. The third, perpendicularly oriented $p$ orbital is a nonbonding $p$ orbital. We can see this orbital (HOMO) in the middle of this diagram from flickr.com:

enter image description here

In contrast, carbon dioxide does have the $p$ orbitals on the central carbon atom interacting strongly with out-of-plane orbitals on the oxygen atoms forming the familiar $\pi$ bonds.

Now let's look at titanium dioxide. Titanium dioxide may come in different phases depending on temperature and pressure, but the phase we generally see under ambient conditions is the rutile structure by WP user Ben Mills:

enter image description here

The red atoms are the oxygen atoms in titanium dioxide, and these are seen to have a distorted, but planar, triangular coordination with the gray titanium atoms (an equilateral triangular coordination does not fit with the octahedral coordination of the titanium). The anatase form described in the OP's reference has a more complex atomic arrangement but similar triangular coordination around each oxygen atom. So, there are perpendicularly oriented $p$ orbitals. The titanium atoms also have out-of-plane orbitals, but unlike the carbon in carbon dioxide these do not interact strongly with the out-of-plane oxygen $p$ orbitals. The difference in orbital energy and size is too great. So the out-of-plane oxygen $p$ orbitals are more like their counterparts in water, essentially nonbonding.

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