By Magdolna Hargittai, Istvan Hargittai
Read or Download Advances in Molecular Structure Research, Volume 3, First Edition (Advances in Molecular Structure Research) PDF
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Extra info for Advances in Molecular Structure Research, Volume 3, First Edition (Advances in Molecular Structure Research)
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Both assume isotopomer-independent vibrational corrections, the former implicitly by fitting isotopic differences of moments, the latter explicitly. When in the set of available isotopomers all atomic positions have been individually substituted at least once, a third and probably more refined method can be applied to obtain the rPm -structure where the vibrational corrections are assumed proportional to the inertial moments, the proportionality factor for all isotopomers being derived from the parent's rs-structure.
RUDOLPH Table 20. 2024(1) 177 Note: aWithoffset correction. C). Later, ground state constants were obtained for the isotopic species FI2c----13CF from ground state combination differences of the v3 and v2 + v3 bands [121]. From the two rotational constants, it is possible to determine the ro structure. On the other hand, to obtain the re structure, it is necessary to make an assumption on the variation of e with isotopic substitution. C). Actually, since e is very small, the result should not be sensitive to the exact value of n.
The more recent robust methods which are able to deal with non-normal errors might give more reliable results and hence deserve further attention. However, it should be noted that if outliers and extreme situations are absent, the "robust" results hardly differ from those of the more conventional method. C. Collinearity or Ill-Conditioning It often happens that some parameters cannot be estimated with precision and that they are very sensitive to small perturbations in the data. This is due to "collinearity" or, more exactly, to the near-collinearity of the fit vector subspace spanned by p column vectors of the Jacobian matrix X in error space (the ndimensional space of the vectors of the observations and of their residuals, y and e, respectively).
