Thursday, December 5, 2019

hybridization - Why is one lobe of an sp3 hybridized orbital smaller than its other half?


A hybrid sp3 orbital is drawn with one lobe smaller than its other half, the latter which is of equal size when drawing the p orbital. Why is it so?



Answer



When combined at a given atomic center, any two atomic orbitals add in a vectorial manner. For example, consider the orbital $\phi$ defined by $\ce{p_{x}}$ and $\ce{p_{y}}$ atomic orbitals as


\begin{align} \phi = c_1 \ce{p_{x}} + c_2 \ce{p_{y}} \end{align}


The orbital addition can be pictured like this


enter image description here



for the two cases $c_1 = c_2 > 0$ and $c_l = -c_2 > 0$, respectively. The ratio $c_1 / c_2$ controls how much the orbital $\phi$ is tilted away from the $x$ (or $y$) axis.


The mixing of atomic orbitals with different angular momentum quantum number is also controlled by a vectorial addition and leads to various types of hybrid orbitals some examples of which are shown here:


enter image description here


The example a) would be an $\ce{sp}$ hybrid orbital. It gets its sense of direction from the $\ce{p}$ orbital used to construct it because the $\ce{s}$ orbital is isotropic. Its shape comes about because the parts of the orbitals that have an opposite sign (this is hinted at by the shading in the pictures) cancel each other out to some extent. So, if the left lobe of the $\ce{p}$ orbital is negativ and the right one is positive and the $\ce{s}$ orbital is also positive then the left half of the $\ce{s}$ orbital overlaps with the left lobe of the $\ce{p}$ orbital in a destructive manner and they cancel each other out, such that only a small portion of the initial $\ce{p}$ orbital lobe remains. But the right half of the $\ce{s}$ orbital overlaps with the right lobe of the $\ce{p}$ orbital in a constructive manner and so the right lobe of the initial $\ce{p}$ orbital becomes larger.


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