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Locally dense basis sets for chemical shift calculations
Author(s) -
Chesnut D. B.,
Moore K. D.
Publication year - 1989
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.540100507
Subject(s) - basis set , basis (linear algebra) , valence (chemistry) , nitrogen , chemistry , atomic physics , atom (system on chip) , molecule , chemical shift , carbon fibers , carbon atom , oxygen atom , fluorine , molecular physics , computational chemistry , materials science , physics , density functional theory , mathematics , geometry , computer science , organic chemistry , alkyl , composite number , embedded system , composite material
Calculations of chemical shifts have been carried out using “locally dense” basis sets for the resonant atom of interest, and smaller, attenuated sets on other atoms in the molecule. For carbon, calculations involving a 6‐311G( d ) triply split valence set with polarization on the resonant atom and 3‐21G atomic bases on other heavy atoms result in good agreement with experiment, and are virtually identical to those found employing the larger basis on all atoms. For species such as nitrogen, oxygen, and fluorine where standard balanced basis sets do not agree well with experiment, use of attenuated sets fail as well. The use of locally dense basis sets permits calculations previously impractical, and the successful application to carbon suggests that the chemical shift is most dependent on the local basis set, and less so on whether or not a balanced or unbalanced calculation is being carried out.