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Double hybrid density-functional theory using the coulomb-attenuating method.
- Source :
- International Journal of Quantum Chemistry; Sep2014, Vol. 114 Issue 18, p1199-1211, 14p
- Publication Year :
- 2014
-
Abstract
- A double hybrid approximation using the Coulomb-attenuating method (CAM-DH) is derived within range-separated density-functional perturbation theory, in the spirit of a recent work by Cornaton et al. (Phys. Rev. A 2013, 88, 022516). The energy expression recovered through second order is linear in the parameters α and β that control the Coulomb attenuation. The method has been tested within the local density approximation on a small test set consisting of rare-gas and alkaline-earth-metal dimers as well as diatomics with single, double, and triple bonds. In this context, the semiempirical α = 0.19 and β = 0.46 parameters, which were optimized for the hybrid CAM-B3LYP functional, do not provide accurate interaction and total energies. Using semilocal functionals with density scaling, which was neglected in this work, may lead to different conclusions. Calibration studies on a larger test set would be necessary at this point. This is left for future work. Finally, we propose as a perspective, an alternative CAM-DH approach that relies on the perturbation expansion of a partially long-range-interacting wavefunction. In this case, the energy is not linear anymore in α and β. Work is in progress in this direction. © 2014 Wiley Periodicals, Inc. [ABSTRACT FROM AUTHOR]
Details
- Language :
- English
- ISSN :
- 00207608
- Volume :
- 114
- Issue :
- 18
- Database :
- Complementary Index
- Journal :
- International Journal of Quantum Chemistry
- Publication Type :
- Academic Journal
- Accession number :
- 97319324
- Full Text :
- https://doi.org/10.1002/qua.24682