Assessing the accuracy of the van der Waals density functionals for rare-gas and small molecular systems

Callsen, Martin; Hamada, Ikutaro

doi:10.1103/physrevb.91.195103

Cited by 42 publications

(26 citation statements)

References 65 publications

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“…Correspondingly, 6 × 6 × 1, 4 × 4 × 1, and 3 × 3 × 1 k points are sampled in the Brillouin zone, respectively. The dispersion forces are included through the self-consistent [26][27][28][29] vdW-DF method [21,22] with the rev-vdW-DF2 functional [30][31][32][33][34][35]. The lattice constant of graphene obtained with the functional is 2.46Å, in good agreement with experiments [36].…”

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confidence: 57%

Hybrid image potential states in molecular overlayers on graphene

Wella

Sawada

Kawaguchi

et al. 2017

Phys. Rev. Materials

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The structural and electronic properties of naphthalene adsorbed on graphene are studied from first principles using the van der Waals density functional method. It is shown that naphthalene molecules are stabilized by forming a superstructure with the periodicity of (2 √ 3 × 2 √ 3) and a tilted molecular adsorption geometry on graphene, in good agreement with the scanning tunneling microscopy (STM) experiments on highly oriented pyrolytic graphite. Our results predict that image potential states (IPSs) are induced by intermolecular interaction on the naphthalene overlayer, hybridizing with the IPSs derived from graphene. The resultant hybrid IPSs are characterized by anisotropic effective mass reflecting the molecular structure of naphthalene. By means of STM simulations, we reveal that one of the hybrid IPSs manifests itself as an oval protrusion distinguishable from naphthalene molecular orbitals, which identifies the origin of an experimental STM image previously attributed to the lowest unoccupied molecular orbital of naphthalene.

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supporting

confidence: 57%

Hybrid image potential states in molecular overlayers on graphene

Wella

Sawada

Kawaguchi

et al. 2017

Phys. Rev. Materials

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“…We compared the performance of three functionals, namely revPBE-vdW [66], used as a reference in Ref. [52], its optimized version optPBE [85,86,87] and a new second-generation rev-vdW-DF2 functional of Hamada [88,89]. In a first series of calculations, we benchmarked the performance of these functionals on the S22 set of weaklyinteracting molecular dimers [90].…”

Section: Resultsmentioning

confidence: 99%

Adsorption of Amino Acids on Gold: Assessing the Accuracy of the GolP-CHARMM Force Field and Parametrization of Au–S Bonds

Futera

Blumberger

2018

J. Chem. Theory Comput.

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The interaction of amino acids with metal electrodes plays a crucial role in bioelectrochemistry and the emerging field of bionanoelectronics. Here we present benchmark calculations of the adsorption structure and energy of all natural amino acids on Au(111) in vacuum using a van-der-Waals density functional (revPBE-vdW) that showed good performance on the S22 set of weakly bound dimers (mean relative unsigned error (MRUE) wrt CCSD(T)/CBS = 13.3%) and adsorption energies of small organic molecules on Au(111) (MRUE wrt experiment = 11.2%). The vdW-DF results are then used to assess the accuracy of a popular force field for Au-amino acid interactions, GolP-CHARMM, which explicitly describes image charge interactions via rigid-rod dipoles. We

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“…[50]; for vdW approaches based on interatomic pairwise potentials, we use Fritz-Haber-Institut (FHI) norm-conserving (NC) pseudopotentials (PPs) [83] because these corrections are not compatible with USPPs in the present version of QE. Following a prior successful approach with vdW density functionals [84], we use Perdew-Burke-Ernzerhof (PBE) [85] PPs for DF2 and DF and PBEsol [86] PPs for DF-cx [62]. In principle, native vdW-PPs have begun to be explored with vdW-DFs, and we relegate the evaluation of such pseudopotentials for acenes to future work [87].…”

Section: Computational Detailsmentioning

confidence: 99%

Structural and excited-state properties of oligoacene crystals from first principles

et al. 2016

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Molecular crystals are a prototypical class of van der Waals (vdW) bound organic materials with excitedstate properties relevant for optoelectronics applications. Predicting the structure and excited-state properties of molecular crystals presents a challenge for electronic structure theory, as standard approximations to density functional theory (DFT) do not capture long-range vdW dispersion interactions and do not yield excited-state properties. In this work, we use a combination of DFT including vdW forces, using both nonlocal correlation functionals and pairwise correction methods, together with many-body perturbation theory (MBPT) to study the geometry and excited states, respectively, of the entire series of oligoacene crystals, from benzene to hexacene. We find that vdW methods can predict lattice constants within 1% of the experimental measurements, on par with the previously reported accuracy of pairwise approximations for the same systems. We further find that excitation energies are sensitive to geometry, but if optimized geometries are used MBPT can yield excited-state properties within a few tenths of an eV from experiment. We elucidate trends in MBPT-computed charged and neutral excitation energies across the acene series and discuss the role of common approximations used in MBPT.

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Assessing the accuracy of the van der Waals density functionals for rare-gas and small molecular systems

Cited by 42 publications

References 65 publications

Hybrid image potential states in molecular overlayers on graphene

Hybrid image potential states in molecular overlayers on graphene

Adsorption of Amino Acids on Gold: Assessing the Accuracy of the GolP-CHARMM Force Field and Parametrization of Au–S Bonds

Structural and excited-state properties of oligoacene crystals from first principles

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