Hesselmann, Andreas and Jansen, Georg and Schuetz, Martin (2005) Density-functional theory-symmetry-adapted intermolecular perturbation theory with density fitting: A new efficient method to study intermolecular interaction energies. JOURNAL OF CHEMICAL PHYSICS, 122 (1): 014103. ISSN 0021-9606, 1089-7690
Full text not available from this repository. (Request a copy)Abstract
The previously developed DFT-SAPT approach, which combines symmetry-adapted intermolecular perturbation theory (SAPT) with a density-functional theory (DFT) representation of the monomers, has been implemented by using density fitting of two-electron objects. This approach, termed DF-DFT-SAPT, scales with the fifth power of the molecular size and with the third power upon increase of the basis set size for a given dimer, thus drastically reducing the cost of the conventional DFT-SAPT method. The accuracy of the density fitting approximation has been tested for the ethyne dimer. It has been found that the errors in the interaction energies due to density fitting are below 10(-3) kcal/mol with suitable auxiliary basis sets and thus one or two orders of magnitude smaller than the errors due to the use of a limited atomic orbital basis set. An investigation of three prominent structures of the benzene dimer, namely, the T shaped, parallel displaced, and sandwich geometries, employing basis sets of up to augmented quadruple-zeta quality shows that DF-DFT-SAPT outperforms second-order Moller-Plesset theory (MP2) and gives total interaction energies which are close to the best estimates infered from combining the results of MP2 and coupled-cluster theory with single, double, and perturbative triple excitations. (C) 2005 American Institute of Physics.
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | KOHN-SHAM ORBITALS; VAN-DER-WAALS; BENZENE DIMER; BASIS-SETS; DISPERSION ENERGIES; CO; APPROXIMATIONS; ACETYLENE; MODEL; MP2; |
| Subjects: | 500 Science > 540 Chemistry & allied sciences |
| Divisions: | Chemistry and Pharmacy > Institut für Physikalische und Theoretische Chemie > Research Group Theoretical Chemistry > Prof. Dr. Martin Schütz |
| Depositing User: | Dr. Gernot Deinzer |
| Date Deposited: | 02 Jun 2021 14:15 |
| Last Modified: | 02 Jun 2021 14:15 |
| URI: | https://pred.uni-regensburg.de/id/eprint/36728 |
Actions (login required)
 |
View Item |
