✦ LIBER ✦

On the validity of polarization and correlation additivity in ab initio molecular orbital calculations

✍ Scribed by Michael J. S. Dewar; Andrew J. Holder

Publisher: John Wiley and Sons
Year: 1990
Tongue: English
Weight: 301 KB
Volume: 11
Category: Article
ISSN: 0192-8651
DOI: 10.1002/jcc.540110305

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✦ Synopsis

A common approximation used in ab initio molecular orbital calculations assumes that the changes in energy due to use of a larger basis set (as in the inclusion of polarization orbitals) and to allowance for electron correlation are additives. Thus, small basis sets may be used for correlated ab initio calculations, resulting in a great savings in time. While this approach has been shown to perform acceptably in some cases, a systematic study has not been published. We examined 35 species and computed the heats of reaction for 15 processes at the 6-31G level of theory using polarization and correlation correction up to the MP4 level. The same items were then treated by an additive procedure to attain the same level of theory. We also examined the conrotrary ring opening of cyclobutene. Our results indicate that the errors do cancel to some extent but that the uncertainty associated with open shell species is significantly larger than closed shell systems. This calls into question the use of the procedure in predicting the properties of transition states.

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