Sunday, November 5, 2017

physical chemistry - What is the biggest known difference between rₑ and r₀?



What is the biggest known difference between $r_e$ and $r_0$? Where $r_0$ is the average bond length of the lowest vibrational state, and $r_e$ is the location where the potential is lowest.


For a perfect harmonic oscillator, these are the same (notice that the peak probability is exactly at the minimum of the potential):


peak probability of lowest vibrational state and harmonic oscillator


What is the largest known difference between $r_e$ and $r_0$ in a real molecule?


This is important because the CRC Handbook on Chemistry and Physics almost always gives $r_0$ because that's what can be determined more easily from experiment, but ab initio geometry optimization almost always gives $r_e$, yet many publications do not even say which type of bond length they are reporting.




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