When Is the Substitution Structure Not Reliable?

Highly precise rotational constants are often used in the substitution method (through Kraitchman's equations) to calculate atomic coordinates with an allegedly marvelous precision. The accuracy of Kraitchman's equations is investigated and it is found that it deteriorates when the mass of...

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Bibliographic Details
Published in:Journal of molecular spectroscopy 2002-09, Vol.215 (1), p.78-84
Main Authors: Demaison, J, Rudolph, H.D
Format: Article
Language:English
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Summary:Highly precise rotational constants are often used in the substitution method (through Kraitchman's equations) to calculate atomic coordinates with an allegedly marvelous precision. The accuracy of Kraitchman's equations is investigated and it is found that it deteriorates when the mass of the molecule increases, the smallest coordinates being the least accurate as expected, but also coordinates larger than 0.5 Å might be badly in error. This explains the discrepant results found in the literature for many large molecules. A possible remedy to this problem is to use the mass-dependent methods.
ISSN:0022-2852
1096-083X
DOI:10.1006/jmsp.2002.8610