Heßelmann A (2008)
Publication Type: Journal article
Publication year: 2008
Book Volume: 128
Article Number: 144112
Journal Issue: 14
DOI: 10.1063/1.2905808
The supermolecular second order Møller-Plesset (MP2) intermolecular interaction energy is corrected by employing time-dependent density functional (TDDFT) response theory. This is done by replacing the uncoupled second order dispersion contribution contained in the supermolecular MP2 energy with the coupled dispersion energy obtained from the TDDFT approach. Preliminary results for the rare gas dimers He2, Ne2, and Ar2 and a few structures of the (HF)2 and (H2O)2 dimers show that the conventional MP2 interaction energies are considerably improved by this procedure if compared to coupled cluster singles doubles with perturbative triples [CCSD(T)] interaction energies. However, the quality of the interaction energies obtained in this way strongly depends on the exchange-correlation potential employed in the monomer calculations: It is shown that an exact exchange-only potential surprisingly often performs better than an asymptotically corrected hybrid exchange-correlation potential. Therefore the method proposed in this work is similar to the method by Cybulski and Lytle [J. Chem. Phys., 127, 141102 (2007)] which corrects the supermolecular MP2 energies with a scaled dispersion energy from time-dependent Hartree--Fock. The results in this work are also compared to the combination of density functional theory and intermolecular perturbation theory.
APA:
Heßelmann, A. (2008). Improved supermolecular second order Mo̸ller-Plesset intermolecular interaction energies using time-dependent density functional response theory. Journal of Chemical Physics, 128(14). https://dx.doi.org/10.1063/1.2905808
MLA:
Heßelmann, Andreas. "Improved supermolecular second order Mo̸ller-Plesset intermolecular interaction energies using time-dependent density functional response theory." Journal of Chemical Physics 128.14 (2008).
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