A second-generation range-separated hybrid van der Waals density functional

Kavli Affiliate: Jeffrey B. Neaton

| First 5 Authors: Vivekanand Shukla, Yang Jiao, Jung-Hoon Lee, Elsebeth Schroder, Jeffrey B. Neaton

| Summary:

We define, test, and illustrate use of a range-separated (screened) hybrid,
termed vdW-DF2-ahbr and abbreviated AHBR, that uses the second-generation
nonlocal-correlation formulation [PRB {bf 82}, 081101(R) (2010)] within the
van der Waals density functional (vdW-DF) method [ROPP {bf 78}, 066501
(2015)]. It supplements the vdW-DF-ahcx [JPCM {bf 34}, 025902 (2022)] (abbreviated AHCX) which relies on the first general-geometry formulation of
the nonlocal correlation energy [PRL 92, 246401 (2004)]. We build the AHBR off
a new analytical-hole analysis of the exchange in vdW-DF2-b86r [PRB {bf 89},
121103 (2014)]. Like AHCX, the AHBR uses an exchange enhancement with a
large-gradient behavior that prevents spurious exchange binding and with a
small-gradient form that is set from many-body perturbation analysis. Unlike
AHCX, however, the AHBR relies on a slightly different interpretation of this
input, moving the resulting exchange description closer to PBEsol exchange [PRL
{bf 100}, 136406 (2008)]. We validate that the range-separated hybrid (RSH)
vdW-DF AHBR retains and exceeds the strong AHCX performance both on bulk and in
a complete planewave benchmarking across the full GMTKN55 suite on broad
molecular properties [PCCP {bf 19}, 32184 (2017)]. Interestingly, the AHBR
accuracy gains are most pronounced for the class of barrier-heights benchmarks,
suggesting that the AHBR is evenly robust for transition-state and binding
properties. Finally, we show that AHBR correctly predicts DNA base-pair
stacking energies, the binding-site preference for CO/Pt(111), and CO$_2$
adsorption in Mg-MOF74.

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