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Auxiliary basis sets for density-fitted correlated wavefunction calculations: weighted core-valence and ECP basis sets for post-d elements.

Authors :
Hättig C
Schmitz G
Kossmann J
Source :
Physical chemistry chemical physics : PCCP [Phys Chem Chem Phys] 2012 May 14; Vol. 14 (18), pp. 6549-55. Date of Electronic Publication: 2012 Mar 28.
Publication Year :
2012

Abstract

We report optimised auxiliary basis sets for the resolution-of-the-identity (or density-fitting) approximation of two-electron integrals in second-order Møller-Plesset perturbation theory (MP2) and similar electronic structure calculations with correlation-consistent basis sets for the post-d elements Ga-Kr, In-Xe, and Tl-Rn. The auxiliary basis sets are optimised such that the density-fitting error is negligible compared to the one-electron basis set error. To check to which extent this criterion is fulfilled we estimated for a test set of 80 molecules the basis set limit of the correlation energy at the MP2 level and evaluated the remaining density-fitting and the one-electron basis set errors. The resulting auxiliary basis sets are only 2-6 times larger than the corresponding one-electron basis sets and lead in MP2 calculations to speed-ups of the integral evaluation by one to three orders of magnitude. The density-fitting errors in the correlation energy are at least hundred times smaller than the one-electron basis set error, i.e. in the order of only 1-100 μH per atom.<br /> (This journal is © the Owner Societies 2012)

Details

Language :
English
ISSN :
1463-9084
Volume :
14
Issue :
18
Database :
MEDLINE
Journal :
Physical chemistry chemical physics : PCCP
Publication Type :
Academic Journal
Accession number :
22456716
Full Text :
https://doi.org/10.1039/c2cp40400a