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Basis sets for transition metals: Optimized outer p functions
Author(s) -
Couty Marc,
Hall Michael B.
Publication year - 1996
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/(sici)1096-987x(199608)17:11<1359::aid-jcc9>3.0.co;2-l
Subject(s) - basis (linear algebra) , transition metal , computational chemistry , computer science , chemistry , statistical physics , mathematics , physics , geometry , organic chemistry , catalysis
Although the ( n + 1) p orbital is unoccupied in transition‐metal ground‐state configurations which are all nd x ( n + 1) s y , these ( n + 1) p functions play a crucial role in the structure of transition metal complexes. As we show here, the usual solution, adding one or more diffuse functions, can be insufficient to create an orbital of the correct energy. The major problem appears to be due to the incorrect placement of the ( n + 1) p orbital's node. Even splitting the most diffuse component of the np orbital and adding a second diffuse function does not completely solve this problem. Although one can usually solve this deficiency by further uncontracting of the np function, here we offer a set of properly optimized ( n + 1) p functions that offer a more compact and satisfactory solution to the proper placements of the node. We show an example of the common deficiencies seen in typical basis sets, including standard basis sets in GAUSSIAN94, and show that the new optimized ( n + 1) p function performs well compared to a fully uncontracted basis set. © 1996 by John Wiley & Sons, Inc.