Noncovalent Interactions in Density-Functional Theory

  title={Noncovalent Interactions in Density-Functional Theory},
  author={Gino A. DiLabio and Alberto Otero-de-la-Roza},
  journal={arXiv: Chemical Physics},
Non-covalent interactions are essential in the description of soft matter, including materials of technological importance and biological molecules. In density-functional theory, common approaches fail to describe dispersion forces, an essential component in noncovalent binding interactions. In the last decade, great progress has been made in the development of accurate and computationally-efficient methods to describe noncovalently bound systems within the framework of density-functional… 

Modeling Soft Supramolecular Nanostructures by Molecular Simulations

The design and assembly of soft supramolecular structures based on small building blocks are governed by non-covalent interactions, selective host-guest interactions, or a combination of different

Chapter 2 Modeling Soft Supramolecular Nanostructures by Molecular Simulations

This chapter provides an overview of the available MD-based methods, including path-based and alchemical free-energy calculations, and practical instructions are introduced on the selection of methods and post-treatment procedures.

Modeling Soft Supramolecular Nanostructures by Molecular Simulations Modeling Soft Supramolecular Nanostructures by Molecular Simulations

The design and assembly of soft supramolecular structures based on small building blocks are governed by non-covalent interactions, selective host-guest interactions, or a combination of different

Application of XDM to ionic solids: The importance of dispersion for bulk moduli and crystal geometries.

The exchange-hole dipole moment model's ability to describe the relative stability, geometry, and compressibility of simple ionic solids is examined and the calculation of bulk moduli for alkali halides and alkaline-earth oxides is considered.

Solid-State Testing of a Van-Der-Waals-Corrected Exchange-Correlation Functional Based on the Semiclassical Atom Theory

The SG4 generalized gradient approximation is extended, developed for covalent and ionic solids with a nonlocal van der Waals functional, and shows a promising applicability for solid-state applications.

Transferable Atom-Centered Potentials for the Correction of Basis Set Incompleteness Errors in Density-Functional Theory.

A correction for BSIE in DFT calculations using basis set incompleteness potentials (BSIP) is developed, which are atom-based one-electron potentials with the same functional form as effective core potentials(ECP) that are designed to correct the effects ofBSIE in properties that are linear mappings of the energy.

Dispersion-Corrected Mean-Field Electronic Structure Methods.

This Review describes the recent developments (including some historical aspects) of dispersion corrections with an emphasis on methods that can be employed routinely with reasonable accuracy in large-scale applications.

Performance of small basis set Hartree–Fock methods for modeling non-covalent interactions

Non-covalent interactions (NCIs) play an essential role in (bio)chemistry. Wavefunction-based methods combined with large basis sets are able to accurately describe inter-and intra-molecular NCIs but

Dispersion corrections applied to the TCA family of exchange-correlation functionals

Dispersion corrections, namely the D3 and VV10 methodologies, have been added to the TCA GGA-like family of functionals. Without corrections, these functionals give very good results for



Dispersion interactions in density‐functional theory

Density-functional theory (DFT) allows for the calculation of many chemical properties with relative ease, thus making it extremely useful for the physical organic chemistry community to understand

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

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

A benchmark for non-covalent interactions in solids.

The recently implemented exchange-hole dipole moment (XDM) model is compared with other approaches in the literature to find that XDM roughly doubles the accuracy of DFT-D2 and non-local functionals in computed lattice energies while, at the same time, predicting cell geometries within less than 2% of the experimental result on average.

Nonlocal van der Waals density functional: the simpler the better.

A nonlocal correlation energy functional that describes the entire range of dispersion interactions in a seamless fashion using only the electron density as input is devised, exhibiting an outstanding precision at predicting equilibrium intermonomer separations in van der Waals complexes.

Exchange-correlation functional with broad accuracy for metallic and nonmetallic compounds, kinetics, and noncovalent interactions.

By incorporating kinetic-energy density in a balanced way in the exchange and correlational functionals and removing self-correlation effects, we have designed a density functional that is broadly

van der Waals Interactions in Density-Functional Theory: Intermolecular Complexes

In previous work (J. Chem. Theory Comput. 2009, 5, 719), we assessed the performance of standard semilocal exchange-correlation density functionals plus the nonempirical dispersion model of Becke and

Semiempirical van der Waals correction to the density functional description of solids and molecular structures

The influence of a simple semiempirical van der Waals (vdW) correction on the description of dispersive, covalent, and ionic bonds within density functional theory is studied. The correction is based

A density-functional model of the dispersion interaction.

A density-functional model depending only on total density, the gradient and Laplacian of the density, and the kinetic-energy density performs as well as the explicitly orbital-dependent model, yet offers obvious computational advantages.

Modeling noncovalent radical-molecule interactions using conventional density-functional theory: beware erroneous charge transfer.

The present results illustrate that the charge-transfer problem is much broader than may have been previously expected and is not limited to conventional (i.e., molecule-molecule) donor-acceptor complexes.

A unified density-functional treatment of dynamical, nondynamical, and dispersion correlations.

A simple solution is proposed resulting in an exact-exchange-based energy functional for all chemical interactions, from the weakest (dispersion) to the strongest (molecular bonds).