Derivation of the orbital analysis equation and its physical significance

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SUMMARY

The discussion centers on the derivation of the orbital analysis equation, specifically $$\cos\theta = \frac{s}{s-1}$$, where ##\theta## represents the bond angle, and ##s## denotes the fractional s-character of the orbital. The equation is crucial for demonstrating that the s-character of axial orbitals in an ##sp^3d## hybridized orbital is zero, thereby supporting Bent's rule, which states that the most electronegative element occupies axial positions in a trigonal bipyramid. Participants express confusion regarding the equation's validity, particularly when ##s>0.5##, and discuss its implications in hybridization theory.

PREREQUISITES
  • Understanding of hybridization concepts, particularly ##sp^3d## hybridization.
  • Familiarity with bond angles and their relationship to orbital character.
  • Knowledge of Bent's rule and its significance in molecular geometry.
  • Basic grasp of trigonometric functions as they apply to molecular orbital theory.
NEXT STEPS
  • Research the formal proof of the equation $$\cos\theta = \frac{s}{s-1}$$ in the context of hybridization.
  • Study the implications of Bent's rule in molecular geometry and its applications.
  • Explore Dragos' rule and its relevance to hybridization and bond angles.
  • Examine the limitations of hybridization models, particularly in non-standard cases.
USEFUL FOR

Chemistry students, molecular theorists, and educators seeking to deepen their understanding of hybridization and its mathematical representations in molecular geometry.

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TL;DR
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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