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Issue 18, 2012
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Auxiliary basis sets for density-fitted correlated wavefunction calculations: weighted core-valence and ECP basis sets for post-d elements

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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.

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

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Publication details

The article was received on 09 Feb 2012, accepted on 11 Mar 2012 and first published on 13 Mar 2012


Article type: Paper
DOI: 10.1039/C2CP40400A
Citation: Phys. Chem. Chem. Phys., 2012,14, 6549-6555
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    Auxiliary basis sets for density-fitted correlated wavefunction calculations: weighted core-valence and ECP basis sets for post-d elements

    C. Hättig, G. Schmitz and J. Koßmann, Phys. Chem. Chem. Phys., 2012, 14, 6549
    DOI: 10.1039/C2CP40400A

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