Wednesday, January 25, 2017

orbitals - What is the origin of the differences between the MO schemes of O₂ and N₂?


Here are the MO schemes of NX2 (left) and OX2 (right).



Why is the σ-MO formed by the p AOs energetically above the π-MO for NX2 but not for OX2?


Can it be explained this way:
In second period elements with more than a half filled p orbitals, the energy pattern of the MOs is regular.
In second period elements with less than or half filled p orbitals, as the s and p atomic orbitals have similar energies, so the formed σXg MO would have similar energy as σXu, but because of electron cloud repulsion it has a big increase in energy, hence it is above the π orbitals? And this phenomenom is known as sp mixing.



Or am I wrong somewhere? Is my reasoning corret?



Answer



This phenomenon is explained by s-p mixing. All the elements in the second period before oxygen have the difference in energy between the 2s and 2p orbital small enough, so that s-p mixing (combination) can occur lowering the energy of the σ(2s) and σ*(2s) and increasing the energy of the σ(2p) and σ*(2p) molecular orbitals. By moving towards right in a period, the s orbital gets more stabilized than the p orbital and the difference in their energies increases, making the s-p mixing for oxygen much smaller.


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