Extrapolation and Scaling of the DFT-SAPT Interaction Energies toward the Basis Set Limit

0360707 - ÚOCHB 2012 RIV US eng J - Článek v odborném periodiku
Řezáč, J. - Hobza, Pavel
Extrapolation and Scaling of the DFT-SAPT Interaction Energies toward the Basis Set Limit.
Journal of Chemical Theory and Computation. Roč. 7, č. 3 (2011), s. 685-689. ISSN 1549-9618. E-ISSN 1549-9626
Grant CEP: GA MŠMT LC512
Výzkumný záměr: CEZ:AV0Z40550506
Klíčová slova: DFT-SAPT * interaction Energies * scaling to complete basis set limit
Kód oboru RIV: CF - Fyzikální chemie a teoretická chemie
Impakt faktor: 5.215, rok: 2011

The dispersion energy term in the symmetry-adapted perturbation theory based on the density functional theory (DFT-SAPT) converges rather slowly with basis set size. Accurate results for large complexes, where only calculations in small basis sets are practical, can be obtained by extrapolation to the complete basis set limit (CBS). In this paper, we propose an extrapolation scheme with the variable exponent optimized specifically for the DFT-SAPT calculations in correlation-consistent basis sets with diffuse functions. Another way to improve the accuracy term at no additional cost is to scale the dispersion term by a fixed amount. We present the scaling factors averaged over a balanced set of 10 model complexes. The results of these schemes are compared to the high-quality DFT-SAPT/CBS interaction energies in small complexes obtained by fitting to a series of basis sets up to aug-cc-pV5Z and to the CCSD(T)/CBS interaction energies.
Trvalý link: http://hdl.handle.net/11104/0198194