Subsystem density‐functional theory (update)

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Abstract

The past years since the publication of our review on subsystem density‐functional theory (sDFT) ( WIREs Comput Mol Sci. 2014, 4:325–362) have witnessed a rapid development and diversification of quantum mechanical fragmentation and embedding approaches related to sDFT and frozen‐density embedding (FDE). In this follow‐up article, we provide an update addressing formal and algorithmic work on sDFT/FDE, novel approximations developed for treating the non‐additive kinetic energy in these DFT/DFT hybrid methods, new areas of application and extensions to properties previously not accessible, projection‐based techniques as an alternative to solely density‐based embedding, progress in wavefunction‐in‐DFT embedding, new fragmentation strategies in the context of DFT which are technically or conceptually similar to sDFT, and the blurring boundary between advanced DFT/MM and approximate DFT/DFT embedding methods.

This article is categorized under:

Electronic Structure Theory > Density Functional Theory

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A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu.

Stefan Grimme, Jens Antony, Stephan Ehrlich … (2010)

The method of dispersion correction as an add-on to standard Kohn-Sham density functional theory (DFT-D) has been refined regarding higher accuracy, broader range of applicability, and less empiricism. The main new ingredients are atom-pairwise specific dispersion coefficients and cutoff radii that are both computed from first principles. The coefficients for new eighth-order dispersion terms are computed using established recursion relations. System (geometry) dependent information is used for the first time in a DFT-D type approach by employing the new concept of fractional coordination numbers (CN). They are used to interpolate between dispersion coefficients of atoms in different chemical environments. The method only requires adjustment of two global parameters for each density functional, is asymptotically exact for a gas of weakly interacting neutral atoms, and easily allows the computation of atomic forces. Three-body nonadditivity terms are considered. The method has been assessed on standard benchmark sets for inter- and intramolecular noncovalent interactions with a particular emphasis on a consistent description of light and heavy element systems. The mean absolute deviations for the S22 benchmark set of noncovalent interactions for 11 standard density functionals decrease by 15%-40% compared to the previous (already accurate) DFT-D version. Spectacular improvements are found for a tripeptide-folding model and all tested metallic systems. The rectification of the long-range behavior and the use of more accurate C(6) coefficients also lead to a much better description of large (infinite) systems as shown for graphene sheets and the adsorption of benzene on an Ag(111) surface. For graphene it is found that the inclusion of three-body terms substantially (by about 10%) weakens the interlayer binding. We propose the revised DFT-D method as a general tool for the computation of the dispersion energy in molecules and solids of any kind with DFT and related (low-cost) electronic structure methods for large systems.

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Effect of the damping function in dispersion corrected density functional theory.

Stefan Grimme, Stephan Ehrlich, Lars Goerigk (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. For 12 different functionals, a standard "zero-damping" formula and rational damping to finite values for small interatomic distances according to Becke and Johnson (BJ-damping) has been tested. The same (DFT-D3) scheme for the computation of the dispersion coefficients is used. The BJ-damping requires one fit parameter more for each functional (three instead of two) but has the advantage of avoiding repulsive interatomic forces at shorter distances. With BJ-damping better results for nonbonded distances and more clear effects of intramolecular dispersion in four representative molecular structures are found. For the noncovalently-bonded structures in the S22 set, both schemes lead to very similar intermolecular distances. For noncovalent interaction energies BJ-damping performs slightly better but both variants can be recommended in general. The exception to this is Hartree-Fock that can be recommended only in the BJ-variant and which is then close to the accuracy of corrected GGAs for non-covalent interactions. According to the thermodynamic benchmarks BJ-damping is more accurate especially for medium-range electron correlation problems and only small and practically insignificant double-counting effects are observed. It seems to provide a physically correct short-range behavior of correlation/dispersion even with unmodified standard functionals. In any case, the differences between the two methods are much smaller than the overall dispersion effect and often also smaller than the influence of the underlying density functional. Copyright © 2011 Wiley Periodicals, Inc.

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Chemistry with ADF

G. te Velde, F. M. Bickelhaupt, E J Baerends … (2001)

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Author and article information

Contributors

Christoph R. Jacob: (View ORCID Profile)

Johannes Neugebauer: (View ORCID Profile)

Journal

Title: WIREs Computational Molecular Science

Abbreviated Title: WIREs Comput Mol Sci

Publisher: Wiley

ISSN (Print): 1759-0876

ISSN (Electronic): 1759-0884

Publication date Created: January 2024

Publication date (Electronic): January 30 2024

Publication date (Print): January 2024

Volume: 14

Issue: 1

Affiliations

[1 ] Institute of Physical and Theoretical Chemistry, Technische Universität Braunschweig Braunschweig Germany

[2 ] Theoretische Organische Chemie Organisch‐Chemisches Institut, Universität Münster Münster Germany

Article

DOI: 10.1002/wcms.1700

SO-VID: d6896323-2464-4c09-83a9-68fa42358d2f

License:

http://creativecommons.org/licenses/by-nc/4.0/

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