Systematically convergent basis sets for explicitly correlated wavefunctions: The atoms H, He, B-Ne, and Al-Ar

Correlation consistent basis sets have been optimized for use with explicitly correlated F12 methods. The new sets, denoted cc - pV n Z - F 12 ( n = D , T , Q ) , are similar in size and construction to the standard aug - cc - pV n Z and aug - cc - pV ( n + d ) Z basis sets, but the new sets are sho...

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Published in:The Journal of chemical physics 2008-02, Vol.128 (8), p.084102-084102-12
Main Authors: Peterson, Kirk A., Adler, Thomas B., Werner, Hans-Joachim
Format: Article
Language:English
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Summary:Correlation consistent basis sets have been optimized for use with explicitly correlated F12 methods. The new sets, denoted cc - pV n Z - F 12 ( n = D , T , Q ) , are similar in size and construction to the standard aug - cc - pV n Z and aug - cc - pV ( n + d ) Z basis sets, but the new sets are shown in the present work to yield much improved convergence toward the complete basis set limit in MP2-F12/3C calculations on several small molecules involving elements of both the first and second row. For molecules containing only first row atoms, the smallest cc-pVDZ-F12 basis set consistently recovers nearly 99% of the MP2 valence correlation energy when combined with the MP2-F12/3C method. The convergence with basis set for molecules containing second row atoms is slower, but the new DZ basis set still recovers 97%-99% of the frozen core MP2 correlation energy. The accuracy of the new basis sets for relative energetics is demonstrated in benchmark calculations on a set of 15 chemical reactions.
ISSN:0021-9606
1089-7690
DOI:10.1063/1.2831537