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Additional info for Topics in Stereochemistry, Volume 6
Sample text
The effect of solvent has been studied in depth for 101. o Molecularity 241 240 26 26 26 26 26 26,239 238 238 238 238 Ref. 6(30) - - + In T/k);“room temperature” assumed to be 25”. 6 - - eu AS, 181 181 181 181 256 84,257 Ref. 5(30p - - - 168 168 168,175 258 - 158 - - - - 158 Ref.
Nonetheless, these investigations thoroughly characterized and popularized the phenomenon. Quantum mechanical tunneling will be important only for cases with very light substituent atoms, such as the proton, and for relatively low barriers. The ammonia case is thus somewhat singular. Almost all other inversion examples discussed herein may be confidently assumed to occur by the classical kinetic process. Furthermore, we shall limit our discussion to barrier heights (for which the question of tunneling vs.
A general approach to the determination of inversion barriers from vibrational spectra was reported by Kincaid and Henriques (92) in 1940. They used a simple quadratic or parabolic potential (eq. [23]) that overestimates the inversion barrier (V,), as Wall and Glockler (1 6) had discovered earlier in their analysis of ammonia. In eq. [23], the variable x is the distance of the atom X from the Y3 plane in an XY:,molecule, xo is the value of x at equilibrium, and k is (4navap),where Y is the frequency of the vibration leading to inversion, p is the reduced mass of the molecule XY3, M , is the mass of X, and M, is the mass of Y.