# Accurate description of van der Waals complexes by density functional theory including empirical corrections

@article{Grimme2004AccurateDO, title={Accurate description of van der Waals complexes by density functional theory including empirical corrections}, author={Stefan Grimme}, journal={Journal of Computational Chemistry}, year={2004}, volume={25} }

An empirical method to account for van der Waals interactions in practical calculations with the density functional theory (termed DFT‐D) is tested for a wide variety of molecular complexes. As in previous schemes, the dispersive energy is described by damped interatomic potentials of the form C6R−6. The use of pure, gradient‐corrected density functionals (BLYP and PBE), together with the resolution‐of‐the‐identity (RI) approximation for the Coulomb operator, allows very efficient computations…

## 3,648 Citations

Self-consistent implementation of a nonlocal van der Waals density functional with a Gaussian basis set.

- Computer ScienceThe Journal of chemical physics
- 2008

It is shown how vdW-DF can be implemented self-consistently with Gaussian basis functions, and the gradients of the energy with respect to nuclear displacements have been derived and coded, enabling efficient geometry optimizations.

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- ChemistryThe Journal of chemical physics
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A simple, efficient, yet accurate local atomic potential (LAP) approach, named DFT+LAP, for including vdW interactions in the framework of DFT, which enables straightforward quantum simulations, such as ab initio molecular dynamics, on biomolecular systems, as well as on other organic systems.

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- ChemistryPhilosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences
- 2016

It was found that the use of either convergence criterion, 10−6 or 10−8, in Gaussian09, does not affect the accuracy of computed optimal distances and binding energies, and an ultra-fine grid needs to be used when computing accurate energies using generalized gradient approximation functionals.

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- ChemistryJournal of chemical theory and computation
- 2014

The most accurate geometries for both choices of basis functions are obtained with the vdW-DF2 functional, while the most accurate lattice energies are obtained using vdw-DF1 with local atomic orbitals and XDM with planewaves with mean absolute errors of less than 4 kJ/mol.

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- ChemistryJ. Comput. Chem.
- 2007

Results including the empirical dispersion term are clearly superior to all pure density functionals investigated and even surpass the MP2/cc‐pVTZ method.

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- ChemistryJ. Comput. Chem.
- 2011

It is shown by an extensive benchmark on molecular energy data that the mathematical form of the damping function in DFT‐D methods has only a minor impact on the quality of the results and BJ‐damping seems to provide a physically correct short‐range behavior of correlation/dispersion even with unmodified standard functionals.

Van der Waals Interactions in Density-Functional Theory: Rare-Gas Diatomics.

- Physics, ChemistryJournal of chemical theory and computation
- 2009

This work has assessed a variety of exchange GGAs for their ability to reproduce exact Hartree-Fock repulsion energies in rare-gas systems, and finds that PW86 performs remarkably well, giving a simple GGA plus dispersion theory yielding excellent rare- gas interaction curves for pairs involving He through Kr.

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- 2017

The ubiquitous long-range van der Waals interactions play a central role in nearly all biological and modern synthetic materials. Yet the most widely used theoretical method for calculating material…

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- Physics
- 2007

We derive the exchange-correlation potential corresponding to the nonlocal van der Waals density functional [M. Dion, H. Rydberg, E. Schroder, D. C. Langreth, and B. I. Lundqvist, Phys. Rev. Lett.…

Accurate interaction energies at density functional theory level by means of an efficient dispersion correction.

- ChemistryThe Journal of chemical physics
- 2009

It is shown that very good quality interaction energies can be obtained by the proposed method for each of the examined functionals, the overall performance of the TPSS functional being the best, which allows to obtain accurate interaction energies without any need of a damping function for complexes close to their exact equilibrium geometry.

## References

SHOWING 1-10 OF 61 REFERENCES

Empirical correction to density functional theory for van der Waals interactions

- Chemistry
- 2002

An empirical method has been designed to account for the van der Waals interactions in practical molecular calculations with density functional theory. For each atom pair separated at a distance R,…

Estimates of the Ab Initio Limit for π−π Interactions: The Benzene Dimer

- Chemistry
- 2002

State-of-the-art electronic structure methods have been applied to the simplest prototype of aromatic π−π interactions, the benzene dimer. By comparison to results with a large aug-cc-pVTZ basis set,…

How does basis set superposition error change the potential surfaces for hydrogen-bonded dimers?

- Chemistry
- 1996

We describe a simple method to automate the geometric optimization of molecular orbital calculations of supermolecules on potential surfaces that are corrected for basis set superposition error using…

Towards extending the applicability of density functional theory to weakly bound systems

- Physics
- 2001

While the attempts currently in progress in several groups for the rigorous inclusion of dispersion interactions in density functional theory (DFT) calculations mature and evolve into practical…

Dispersion corrections to density functionals for water aromatic interactions.

- ChemistryThe Journal of chemical physics
- 2004

The results indicate that the use of the B3LYP functional in combination with an appropriate mixing rule and damping function is recommended for the interaction of water with aromatics.

From The Cover: The X3LYP extended density functional for accurate descriptions of nonbond interactions, spin states, and thermochemical properties.

- ChemistryProceedings of the National Academy of Sciences of the United States of America
- 2004

The X3LYP (extended hybrid functional combined with Lee-Yang-Parr correlation functional) extended functional for density functional theory is developed to significantly improve the accuracy for hydrogen-bonded and van der Waals complexes while also improving the accuracy in heats of formation, ionization potentials, electron affinities, and total atomic energies.

Describing van der Waals interaction in diatomic molecules with generalized gradient approximations: The role of the exchange functional

- Chemistry
- 1997

Generalized gradient approximations have been used to calculate the potential energy curves for six rare gas diatomic molecules. Several generalized gradient approximations are found to provide a…

High-level ab initio computations of structures and interaction energies of naphthalene dimers: origin of attraction and its directionality.

- ChemistryThe Journal of chemical physics
- 2004

The estimated interaction energies of the set of geometries explored in this work show that two structures emerge as being the lowest energy, and may effectively be considered as isoenergetic on the basis of the errors inherent in out extrapolation procedure.

Electron affinities of the first‐row atoms revisited. Systematic basis sets and wave functions

- Chemistry
- 1992

The calculation of accurate electron affinities (EAs) of atomic or molecular species is one of the most challenging tasks in quantum chemistry. We describe a reliable procedure for calculating the…