Derivation of the orbital analysis equation and its physical significance

AI Thread Summary
The discussion focuses on the equation $$cos\theta = \frac{s}{s-1}$$, which relates bond angles to the s and p character of orbitals, specifically in the context of ##sp^3d## hybridization. It highlights that the equation is used to demonstrate the s-character of axial orbitals is zero and supports Bent's rule regarding electronegativity in trigonal bipyramidal structures. Participants express confusion over the validity of the equation, particularly when s exceeds 0.5, leading to contradictions in cos(θ) values. There is also mention of the equation's lack of popularity and potential misunderstanding regarding hybridization concepts. The conversation concludes with an acknowledgment of the complexities involved in understanding these orbital relationships.
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TL;DR Summary
unable to prove/derive theoretically the relation between bond angle and s and p character of a hybridized orbital.
$$cos\theta = \frac {s}{1-s} = \frac{p-1}{p}$$
in this equation ##\theta## is the bond angle and ##s## and ##p## are the fractional s-character of the orbital and p-character of the orbital.
This is equation is used rigorously in showing that the s-character of the axial orbitals in a ##sp^3d## hybridized orbital is 0 and hence it is also used to prove bents rule which states that the most electronegative element in a ##sp^3d## hybridized orbital takes the axial positions of the trigonal bipyramid that is formed. But I am unable to find a formal proof/derivation of this equation on the internet or in my textbook.
Is this relation between the bond angle and the s/p character very obvious that it does not need a proof/derivation?
(also I am assuming there might be an experimental proof for this formula but I am not looking for that rather a theoretical proof of this equation will be nice)
 
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Can't say this relation makes sense, for s>0.5 cos(θ) would be larger than 1.
 
Borek said:
Can't say this relation makes sense, for s>0.5 cos(θ) would be larger than 1.
I am so sorry I made a typo it is actually $$cos\theta = \frac{s}{s-1}$$
 
Still fails, now for s>0.5.
 
Borek said:
Still fails, now for s>0.5.
I thought it was clear no hybridized orbital can have an s character more than 50%(0.5 fractional) as sp hybridized orbital has the least number of orbitals(2) combining and has 50% s-character in both orbitals. Hence the equation does not fail.
also, this very fact was used in Dragos rule...
 
OK, for "standard", non fractional hybridizations it will hold.

Apparently I know a bit too much to properly understand the problem as defined here.
 
Borek said:
OK, for "standard", non fractional hybridizations it will hold.

Apparently I know a bit too much to properly understand the problem as defined here.
maybe this particular equation isn't very popular(because it isn't very general?)
 
I don't remember being taught it. Doesn't mean much.

On the second thought I could get s and p reversed. My bad.
 
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