Compatibility of correlation-consistent basis sets with a hybrid Hartree-Fock/density functional method

401

268

The performance of the previously proposed polarization consistent basis sets is analyzed at the Hartree-Fock and density functional levels of theory, and it is shown that each step up in basis set quality decreases the error relative to the infinite basis set limit by approximately an order of magnitude. For the largest pc-4 basis set the relative energy error is approximately 10 Ϫ7 , and extrapolation further improves the results by approximately a factor of 2. This provides total atomization energies for molecules with an accuracy of better than 0.01 kJ/mol per atom. The performance of many popular basis sets is evaluated based on 95 atomization energies, 42 ionization potentials and 10 molecular relative energies, and it is shown that the pc-n basis sets in all cases provides better accuracy for a similar or a smaller number of basis functions.

Section: Introductionmentioning

confidence: 99%

Polarization consistent basis sets. II. Estimating the Kohn–Sham basis set limit

Jensen

2002

401

268

“…It has previously been noted that basis set convergence within DFT may be slow. 77,78 We recommend that any systematic study of the performance of a DFT functional should include a study of the basis set effect by going at least to the TZ basis set level.…”

Section: Discussionmentioning

confidence: 99%

On the performance of four-component relativistic density functional theory: Spectroscopic constants and dipole moments of the diatomics HX and XY (X,Y=F, Cl, Br, and I)

Fossgaard

Gropen

Valero

et al. 2003

“…Despite the small changes in energies beyond the triple-level, recent work has shown that nonmonotonic convergence of energetic properties can occur with respect to increasing basis set size for density functional theory. 9,12,17,18 This has been shown for a number of molecules and functionals, with no obvious trends appearing as to when the nonmonotonic convergence does or does not occur. When monotonic convergence behavior occurs, then it has been shown that various extrapolation formulas can be used to estimate the complete basis set limit, or in the case of density functional theory, the Kohn-Sham ͑KS͒ limit.…”

Section: Introductionmentioning

confidence: 92%

Behavior of density functionals with respect to basis set. VI. Truncation of the correlation consistent basis sets

Prascher

Wilson

2007

Systematic truncation of the correlation consistent basis sets has been investigated in first and second row atoms and molecules to better understand basis set requirements for density functional theory, particularly the need for high angular momentum functions, as well as to understand possible computational cost savings that could be achieved by using reduced basis sets. The truncation scheme employed follows that recently introduced for ab initio methods [B. Mintz et al., J. Chem. Phys. 121, 5629 (2004)]. Properties examined in the current study include geometries, ionization potentials, electron affinities, and dissociation energies. In general, this investigation shows that a degree of truncation of higher angular momentum functions is possible with limited impact upon energetic properties, and does result in useful CPU time savings. However, not all properties investigated have the same level of dependence upon high angular momentum functions, and, thus, careful selection of truncated basis sets should be made.