Screening nature of the van der Waals density functional method: A review and analysis of the many-body physics foundation
Reviewartikel, 2020

We review the screening nature and many-body physics foundation of the van der Waals density functional (vdW-DF) method [Berland K et al 2015 Rep. Prog. Phys. 78 066501], a systematic approach to construct truly nonlocal exchange–correlation energy density functionals. To that end we define and focus on a class of consistent vdW-DF versions that adhere to the Lindhard screening logic of the full method formulation. The consistent-exchange vdW-DF-cx version [Berland K and Hyldgaard P 2014 Phys. Rev. B 89 035412] and its spin extension [Thonhauser T et al 2015 Phys. Rev. Lett. 115 136402] represent the first examples of this class; in general, consistent vdW-DFs reflect a concerted expansion of a formal recast of the adiabatic-connection formula [Hyldgaard P et al 2014 Phys. Rev. B 90 075148], an exponential summation of contributions to the local-field response, and the Dyson equation. We argue that the screening emphasis is essential because the exchange–correlation energy reflects an effective electrodynamics set by a long-range interaction. Two consequences are that (1) there are, in principle, no wiggle room in how one balances exchange and correlation, for example, in vdW-DF-cx, and that (2) consistent vdW-DFs have a formal structure that allows them to incorporate vertex-correction effects, at least in the case of levels that experience recoil-less interactions (for example, near the Fermi surface). We explore the extent to which the strictly nonempirical vdW-DF-cx formulation can serve as a systematic extension of the constraint-based semilocal functionals. For validation, we provide a complete survey of vdW-DF-cx performance for broad molecular processes, for the full set of 55 benchmarks in GMTKN55 [Goerigk L et al 2017 Phys. Chem. Chem. Phys. 19 32184] and comparing to the quantum-chemistry calculations that are summarized in that paper. We also provide new vdW-DF-cx results for metal surface energies and work functions that we compare to experiment. Finally, we use the screening insight to separate the vdW-DF nonlocal-correlation term into pure-vdW-interaction and local-field-susceptibility effects and present tools to compute and map the binding signatures.

Författare

Per Hyldgaard

Chalmers, Mikroteknologi och nanovetenskap (MC2), Elektronikmaterial och system

Yang Jiao

Chalmers, Mikroteknologi och nanovetenskap (MC2), Elektronikmaterial och system

Vivekanand Shukla

Chalmers, Mikroteknologi och nanovetenskap (MC2), Elektronikmaterial och system

Journal of Physics Condensed Matter

0953-8984 (ISSN)

Vol. 32 393001-

Ämneskategorier

Oorganisk kemi

Atom- och molekylfysik och optik

Annan fysik

Teoretisk kemi

Organisk kemi

Den kondenserade materiens fysik

Styrkeområden

Nanovetenskap och nanoteknik (SO 2010-2017, EI 2018-)

Produktion

Energi

Livsvetenskaper och teknik (2010-2018)

Materialvetenskap

Fundament

Grundläggande vetenskaper

Infrastruktur

C3SE (Chalmers Centre for Computational Science and Engineering)

DOI

10.1088/1361-648X/ab8250

Mer information

Senast uppdaterat

2020-09-04