Tuesday, August 6, 2019

bond - What does it mean when it is said that an sp³ orbital has 25% s character?


My textbook frequently mentions:



$\mathrm{sp^3}$ hybrid orbital has 25% $\mathrm{s}$-character and 75% $\mathrm{p}$-character.




What are these "characters"? And how do these characters influence the bond and the hybrid orbital?



Answer



Hybridisation is a purely mathematical concept, which makes it possible to explain experimentally found structures. The most prominent example for this is methane, where you can consider the central carbon atom to be $\mathrm{sp^3}$ hybridised. Formally, the $\mathrm{s}$ orbital and the three $\mathrm{p}$ orbitals can be linearly combined to form four equivalent orbitals. Hence $\mathrm{sp^3}$ is a contraction of $\mathrm{s^{\frac{1}{4}}p^{\frac{3}{4}}}$. Therefore you can see, that the orbital has $25\,\%$ $\mathrm{s}$ character and $75\,\%$ $\mathrm{p}$ character.
Generally, the concept of hybridisation has to be treated as a concept only, it is nothing which can be physically observed. It is a mathematical model to understand geometries better. Please also note, that hybridisation is a function of the geometry, not the other way around. Having said that, it is fairly obvious, that I am not a big fan of the concept. I would not go as far as Alexander Grushow* and preach to abandon the whole thing, but I advise caution in the use of this concept to not obtain wrong conclusions.



Despite significant experimental evidence and theoretical advances to indicate that hybrid atomic orbitals do not exist and do not appropriately describe molecular bonding, their description still permeates chemical education at many levels, and the model still finds its way into modern chemical literature.



* “Is It Time To Retire the Hybrid Atomic Orbital?” Alexander Grushow, J. Chem. Educ., 2011, 88 (7), 860–862.


No comments:

Post a Comment

digital communications - Understanding the Matched Filter

I have a question about matched filtering. Does the matched filter maximise the SNR at the moment of decision only? As far as I understand, ...