What are the most efficient basis set strategies for correlated wave function calculations of reaction energies and barrier heights

Ewa Papajak, Donald G. Truhlar

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71 Scopus citations


As electronic structure methods are being used to obtain quantitatively accurate reaction energies and barrier heights for increasingly larger systems, the choice of an efficient basis set is becoming more critical. The optimum strategy for achieving basis set convergence can depend on the way that electron correlation is treated and can take advantage of flexibility in the order in which basis functions are added. Here we study several approaches for estimating accurate reaction energies and barrier heights from post-Hartree-Fock electronic structure calculations. First and second, we evaluate methods of estimating the basis set limit of second order Moller-Plesset perturbation theory and of coupled cluster theory with single and double excitations and a quasiperturbative treatment of connected triple excitations by using explicitly correlated basis functions (in the F12a implementation) along with valence, polarization, and diffuse one-electron basis functions. Third, we test the scheme of adding a higher-order correction to MP2 results (sometimes called MP2CBS ΔCCSD(T)). Finally, we evaluate the basis set requirements of these methods in light of comparisons to Weizmann-3.2, Weizmann-4, and CCSDT(2) QCBSCVR results.

Original languageEnglish (US)
Article number064110
JournalJournal of Chemical Physics
Issue number6
StatePublished - Aug 14 2012

Bibliographical note

Funding Information:
The authors are grateful to Gillian Shaw for preliminary calculations and to Antonio Varandas and Jingjing Zheng for stimulating discussions. This work was supported in part by the U. S. Department of Energy, Office of Basic Energy Sciences (Grant No. DE-FG02-86ER13579). This research was performed in part using the Molecular Science Computing Facility (MSCF) in the William R. Wiley Environmental Molecular Sciences Laboratory, a national scientific user facility sponsored by the U.S. Department of Energy's Office of Biological and Environmental Research and located at the Pacific Northwest National Laboratory, operated for the Department of Energy by Battelle.


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