Extent of Fock-exchange mixing for a hybrid van der Waals density functional?
Artikel i vetenskaplig tidskrift, 2018

The vdW-DF-cx0 exchange-correlation hybrid design [K. Berland et al., J. Chem. Phys. 146, 234106 (2017)] has a truly nonlocal correlation component and aims to facilitate concurrent descriptions of both covalent and non-covalent molecular interactions. The vdW-DF-cx0 design mixes a fixed ratio, a, of the Fock exchange into the consistent-exchange van der Waals density functional, vdW-DF-cx [K. Berland and P. Hyldgaard, Phys. Rev. B 89, 035412 (2014)]. The mixing value a is sometimes taken as a semi-empirical parameter in hybrid formulations. Here, instead, we assert a plausible optimum average a value for the vdW-DF-cx0 design from a formal analysis; A new, independent determination of the mixing a is necessary since the Becke fit [A. D. Becke, J. Chem. Phys. 98, 5648 (1993)], yielding a 0 = 0.2, is restricted to semilocal correlation and does not reflect non-covalent interactions. To proceed, we adapt the so-called two-legged hybrid construction [K. Burke et al., Chem. Phys. Lett. 265, 115 (1997)] to a starting point in the vdW-DF-cx functional. For our approach, termed vdW-DF-tlh, we estimate the properties of the adiabatic-connection specification of the exact exchange-correlation functional, by combining calculations of the Fock exchange and of the coupling-constant variation in vdW-DF-cx. We find that such vdW-DF-tlh hybrid constructions yield accurate characterizations of molecular interactions (even if they lack self-consistency). The accuracy motivates trust in the vdW-DF-tlh determination of system-specific values of the Fock-exchange mixing. We find that an average value a 0 = 0.2 best characterizes the vdW-DF-tlh description of covalent and non-covalent interactions, although there exists some scatter. This finding suggests that the original Becke value, a 0 = 0.2, also represents an optimal average Fock-exchange mixing for the new, truly nonlocal-correlation hybrids. To enable self-consistent calculations, we furthermore define and test a zero-parameter hybrid functional vdW-DF-cx0p (having fixed mixing a 0 = 0.2) and document that this truly nonlocal correlation hybrid works for general molecular interactions (at reference and at relaxed geometries). It is encouraging that the vdW-DF-cx0p functional remains useful also for descriptions of some extended systems. Published by AIP Publishing.

Författare

Yang Jiao

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

Elsebeth Schröder

Chalmers, Mikroteknologi och nanovetenskap (MC2), Kvantkomponentfysik

Per Hyldgaard

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

Journal of Chemical Physics

0021-9606 (ISSN) 1089-7690 (eISSN)

Vol. 148 19 194115

Föroreningspartiklars fysisorption och svaga kemisorption - atomskalig teori och beräkningar

Vetenskapsrådet (VR), 2015-01-01 -- 2018-12-31.

Konsistenta van der Waals täthetsfunktional-studier av bindning, struktur och optisk respons i molekylära energisystem.

Vetenskapsrådet (VR), 2015-01-01 -- 2018-12-31.

Ämneskategorier

Fysikalisk kemi

Atom- och molekylfysik och optik

Annan fysik

Teoretisk kemi

Infrastruktur

C3SE (Chalmers Centre for Computational Science and Engineering)

Styrkeområden

Materialvetenskap

DOI

10.1063/1.5012870