Basis Set Convergence of Molecular Correlation Energy Differences Within the Random Phase Approximation
Document Type
Article
Publication Date
2-28-2012
Abstract
The basis set convergence of energy differences obtained from the random phase approximation (RPA) to the correlation energy is investigated for a wide range of molecular interactions. For dispersion bound systems the basis set incompleteness error is most pronounced, as shown for the S22 benchmark [P. Jurecka, Phys. Chem. Chem. Phys. 8, 1985 (2006)10.1039/b600027d]. The use of very large basis sets ( quintuple-zeta) or extrapolation to the complete basis set (CBS) limit is necessary to obtain a reliable estimate of the binding energy for these systems. Counterpoise corrected results converge to the same CBS limit, but counterpoise correction without extrapolation is insufficient. Core-valence correlations do not play a significant role. For medium- and short-range correlation, quadruple-zeta results are essentially converged, as demonstrated for relative alkane conformer energies, reaction energies dominated by intramolecular dispersion, isomerization energies, and reaction energies of small organic molecules. Except for weakly bound systems, diffuse augmentation almost universally slows down basis set convergence. For most RPA applications, quadruple-zeta valence basis sets offer a good balance between accuracy and efficiency.
DOI
10.1063/1.3687005
Montclair State University Digital Commons Citation
Eshuis, Hendrik and Furche, Filipp, "Basis Set Convergence of Molecular Correlation Energy Differences Within the Random Phase Approximation" (2012). Department of Chemistry and Biochemistry Faculty Scholarship and Creative Works. 306.
https://digitalcommons.montclair.edu/chem-biochem-facpubs/306