A density functional study of van der Waals interactions

Kamiya, Motoshi; Tsuneda, Takao; Hirao, Kimihiko

doi:10.1063/1.1501132

Cited by 260 publications

(202 citation statements)

References 29 publications

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“…12,13). Non-empirical approaches include nonlocal correlation functionals derived from response theory [14][15][16] (possibly combined with long-range corrected exchange functionals [17][18][19]), DFT-based symmetry-adapted intermolecular perturbation theory (see, e.g., Ref. 20) and range-separated density-functional theory (see, e.g., Ref.…”

Section: Introductionmentioning

confidence: 99%

Range-separated density-functional theory with random phase approximation applied to noncovalent intermolecular interactions

Zhu

Toulouse

Savin

et al. 2010

The Journal of Chemical Physics

130

141

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Range-separated methods combining a short-range density functional with long-range random phase approximations (RPA) with or without exchange response kernel are tested on rare-gas dimers and the S22 benchmark set of weakly interacting complexes of Jurečka,Šponer,Černý, and Hobza (Phys. Chem. Chem. Phys. 8, 1985Phys. 8, , 2006. The methods are also compared to full-range RPA approaches. Both range separation and inclusion of the Hartree-Fock exchange kernel largely improve the accuracy of intermolecular interaction energies. The best results are obtained with the method called RSH+RPAx which yields interaction energies for the S22 set with an estimated mean absolute error of about 0.5 -0.6 kcal/mol, corresponding to a mean absolute percentage error of about 7 -9%, depending on the reference interaction energies used. In particular, the RSH+RPAx method is found to be overall more accurate than the range-separated method based on long-range second-order Møller-Plesset (MP2) perturbation theory (RSH+MP2).

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Section: Introductionmentioning

confidence: 99%

Range-separated density-functional theory with random phase approximation applied to noncovalent intermolecular interactions

Zhu

Toulouse

Savin

et al. 2010

The Journal of Chemical Physics

130

141

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“…It has also been shown [34] that the artificial minimum of the rare gas dimer potential curves can be removed by an exact treatment of the long-range exchange.…”

Section: Introductionmentioning

confidence: 99%

van der Waals forces in density functional theory: Perturbational long-range electron-interaction corrections

et al. 2005

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Long-range exchange and correlation effects, responsible for the failure of currently used approximate density functionals in describing van der Waals forces, are taken into account explicitly after a separation of the electronelectron interaction in the Hamiltonian into short-and long-range components. We propose a "range-separated hybrid" functional based on a local density approximation for the short-range exchange-correlation energy, combined with a long-range exact exchange energy. Long-range correlation effects are added by a second-order perturbational treatment. The resulting scheme is general and is particularly well-adapted to describe van der Waals complexes, like rare gas dimers.PACS numbers: 31.15. Ew, 31.15.Ar, 31.15.Md, 71.15.Mb

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“…To explore the S N 2 reaction of Cl − + CH 3 I → CH 3 Cl + I − in further detail, we also carry out the reaction path search calculations using the artificial force induced reaction method in the global reaction route mapping (GRRM) program [30,31] by taking van der Waals (vdW) correlations into consideration. The van der Waals calculation uses the LC+vdW method [32][33][34], which combines LC-DFT with the van der Waals correlation of, e.g., a van der Waals functional. As the van der Waals correlation, we adopt the local response dispersion (LRD) vdW functional [35].…”

Section: Computational Detailsmentioning

confidence: 99%

Orbital Energy-Based Reaction Analysis of SN2 Reactions

et al. 2016

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An orbital energy-based reaction analysis theory is presented as an extension of the orbital-based conceptual density functional theory. In the orbital energy-based theory, the orbitals contributing to reactions are interpreted to be valence orbitals giving the largest orbital energy variation from reactants to products. Reactions are taken to be electron transfer-driven when they provide small variations for the gaps between the contributing occupied and unoccupied orbital energies on the intrinsic reaction coordinates in the initial processes. The orbital energy-based theory is then applied to the calculations of several S N 2 reactions. Using a reaction path search method, the Cl − + CH 3 I → ClCH 3 + I − reaction, for which another reaction path called "roundabout path" is proposed, is found to have a precursor process similar to the roundabout path just before this S N 2 reaction process. The orbital energy-based theory indicates that this precursor process is obviously driven by structural change, while the successor S N 2 reaction proceeds through electron transfer between the contributing orbitals. Comparing the calculated results of the S N 2 reactions in gas phase and in aqueous solution shows that the contributing orbitals significantly depend on solvent effects and these orbitals can be correctly determined by this theory.

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A density functional study of van der Waals interactions

Cited by 260 publications

References 29 publications

Range-separated density-functional theory with random phase approximation applied to noncovalent intermolecular interactions

Range-separated density-functional theory with random phase approximation applied to noncovalent intermolecular interactions

van der Waals forces in density functional theory: Perturbational long-range electron-interaction corrections

Orbital Energy-Based Reaction Analysis of SN2 Reactions

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