Defining the Domain of Density Functionals: Charge-Transfer Complexes

Ruiz, Eliseo; Salahub, Dennis R.; Vela, Alberto García

doi:10.1021/ja00108a036

Cited by 137 publications

(114 citation statements)

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“…4 Strongly bonded systems as well as weakly bonded ones, like hydrogen-bonded systems 5 or charge-transfer complexes, 6 are also described with reasonable accuracy. As the method is particularly cost-effective, it is now widely used as a standard alternative to conventional postHartree-Fock methods.…”

Section: Introductionmentioning

confidence: 88%

A Systematic Failing of Current Density Functionals: Overestimation of Two-Center Three-Electron Bonding Energies

1998

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Several density functional theories, chosen among the most popular, are shown to systematically overestimate three-electron bond dissociation energies in a series of model systems covering the full range of homonuclear three-electron X∴X bonds (X ) He, N, O, F, Ne, P, S, Cl, Ar) that can be found in organic cation radicals. The errors range from 15 to 54 kcal/mol with the SVWN local spin density method, from 6 to 45 kcal/mol with the gradient-corrected BLYP, BP86, and BPW91 functionals, and from 3 to 31 kcal/mol with the B3LYP, B3P86, and B3PW91 three-parameter hybrid functionals. The errors follow some regular tendencies according to the place of the X atom in the periodic table. The geometries and frequencies are also in error, the bond lengths being systematically too long and the frequencies too low. The errors are tentatively interpreted as consequences of electron self-interaction, leading to overstabilization of the Coulombic terms relative to the exchange-correlation terms in this type of bonds. At variance with these systematic errors, the BH&HLYP functional displays overall better results but still severely fails in some particular cases. Some lines of thought for devising modified DFT functionals are proposed.

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Section: Introductionmentioning

confidence: 88%

A Systematic Failing of Current Density Functionals: Overestimation of Two-Center Three-Electron Bonding Energies

1998

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“…Though a previous study for related CTC's in gas phase 49 has shown the difficulties of DFT to reproduce experimental geometry, especially at the local level, no DFT result is available for the corresponding TS structures. Since the TS is much more polar than the CTC, the electrostatic interactions dominate and the influence of density gradient corrections on the geometry is expected to be smaller in that case.…”

Section: Definition Of the Reaction Coordinatementioning

confidence: 99%

Molecular dynamics simulations of elementary chemical processes in liquid water using combined density functional and molecular mechanics potentials. II. Charge separation processes

Strnad

Martins‐Costa

Millot

et al. 1997

The Journal of Chemical Physics

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A new approach to carry out molecular dynamics simulations of chemical reactions in solution using combined density functional theory/molecular mechanics potentials is presented. We focus our attention on the analysis of reactive trajectories, dynamic solvent effects and transmission coefficient rather than on the evaluation of free energy which is another important topic that will be examined elsewhere. In a previous paper we have described the generalities of this hybrid molecular dynamics method and it has been employed to investigate low energy barrier proton transfer process in water. The study of processes with activation energies larger than a few kT requires the use of specific techniques adapted to ''rare events'' simulations. We describe here a method that consists in the simulation of short trajectories starting from an equilibrated transition state in solution, the structure of which has been approximately established. This calculation is particularly efficient when carried out with parallel computers since the study of a reactive process is decomposed in a set of short time trajectories that are completely independent. The procedure is close to that used by other authors in the context of classical molecular dynamics but present the advantage of describing the chemical system with rigorous quantum mechanical calculations. It is illustrated through the study of the first reaction step in electrophilic bromination of ethylene in water. This elementary process is representative of many charge separation reactions for which static and dynamic solvent effects play a fundamental role. © 1997 American Institute of Physics. ͓S0021-9606͑97͒00809-X͔

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“…On the other hand it fails to reproduce nonlocal dispersive forces, in particular van der Waals forces, which are important in weakly bonded materials such as graphite, molecular crystals, and many organic compounds. [7][8][9] It is also well known that the local-density approximation ͑LDA͒ tends to overbind systems where van der Waals interactions are important, while the generalized gradient approximations ͑GGAs͒ usually tend to underestimate the binding in these systems. In the case of graphene on metals many GGAs, contrary to experiments, predict no binding at all, and therefore most theoretical work on graphene-metal interfaces has relied on the LDA.…”

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confidence: 99%

Graphene on metals: A van der Waals density functional study

et al. 2010

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We use density functional theory (DFT) with a recently developed van der Waals density functional (vdW-DF) to study the adsorption of graphene on Al, Cu, Ag, Au, Pt, Pd, Co and Ni(111) surfaces. In constrast to the local density approximation (LDA) which predicts relatively strong binding for Ni,Co and Pd, the vdW-DF predicts weak binding for all metals and metal-graphene distances in the range 3.40-3.72 Å. At these distances the graphene bandstructure as calculated with DFT and the many-body G0W0 method is basically unaffected by the substrate, in particular there is no opening of a band gap at the K-point.

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Defining the Domain of Density Functionals: Charge-Transfer Complexes

Cited by 137 publications

References 1 publication

A Systematic Failing of Current Density Functionals: Overestimation of Two-Center Three-Electron Bonding Energies

A Systematic Failing of Current Density Functionals: Overestimation of Two-Center Three-Electron Bonding Energies

Molecular dynamics simulations of elementary chemical processes in liquid water using combined density functional and molecular mechanics potentials. II. Charge separation processes

Graphene on metals: A van der Waals density functional study

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