Assessment of two hybrid van der Waals density functionals for covalent and non-covalent binding of molecules

Abstract

Two hybrid van der Waals density functionals (vdW-DFs) are constructed using 25%, Fock exchange with i) the consistent-exchange vdW-DF-cx functional and ii) with the vdW-DF2 functional. The ability to describe covalent and non-covalent binding properties of molecules are assessed. For properties related to covalent binding, atomization energies (G2-1 set), molecular reaction energies (G2RC set), as well as ionization energies (G21IP set) are benchmarked against experimental reference values. We find that hybrid-vdW-DF-cx yields results that are rather similar to those of the standard non-empirical hybrid PBE0 [JCP 110, 6158 (1996)]. Hybrid vdW-DF2 follows somewhat different trends, showing on average significantly larger deviations from the reference energies, with a MAD of 14.5 kcal/mol for the G2-1 set. Non-covalent binding properties of molecules are assessed using the S22 benchmark set of non-covalently bonded dimers and the X40 set of dimers of small halogenated molecules, using wavefunction-based quantum chemistry results for references. For the S22 set, hybrid-vdW-DF-cx performs better than standard vdW-DF-cx for the mostly hydrogen-bonded systems. Hybrid-vdW-DF2 offers a slight improvement over standard vdW-DF2. Similar trends are found for the X40 set, with hybrid-vdW-DF-cx performing particularly well for binding involving the strongly polar hydrogen halides, but poorly for systems with tiny binding energies. Our study of the X40 set reveals both the potential of mixing Fock exchange with vdW-DF, but also highlights shortcomings of the hybrids constructed here. The solid performance of hybrid-vdW-DF-cx for covalent-bonded systems, as well as the strengths and issues uncovered for non-covalently bonded systems, makes this study a good starting point for developing even more precise hybrid vdW-DFs.

References in corpus (28)

• Quantum ESPRESSO: a modular and open-source software project for quantum simulations of materials
• Van der Waals Density Functional for General Geometries
• Van der Waals density functionals applied to solids
• A Higher-Accuracy van der Waals Density Functional
• Perspective on density functional theory
• Efficient implementation of a van der Waals density functional: Application to double-wall carbon nanotubes
• Ab initio pseudopotentials for electronic structure calculations of poly-atomic systems using density-functional theory
• Nonlocal van der Waals density functional: The simpler the better
• Van der Waals density functional: Self-consistent potential and the nature of the van der Waals bond
• Perspective: Advances and challenges in treating van der Waals dispersion forces in density functional theory
• van der Waals forces in density functional theory: The vdW-DF method
• Van der Waals Density Functional for Layered Structures
• An exchange functional that tests the robustness of the plasmon description of the van der Waals density functional
• Van der Waals density functional: an appropriate exchange functional
• Application of van der Waals Density Functional to an Extended System: Adsorption of Benzene and Naphthalene on Graphite
• Spin signature of nonlocal-correlation binding in metal organic frameworks
• Benzene Adsorbed on Metals: Concerted Effect of Covalency and van der Waals Bonding
• To wet or not to wet? Dispersion forces tip the balance for water-ice on metals
• Testing several recent van der Waals density functionals for layered structures
• Thermal expansion and transport in van der Waals solids from first-principles calculations
• van der Waals density functionals built upon the electron-gas tradition: Facing the challenge of competing interactions
• An analysis of van der Waals density functional components: Binding and corrugation of benzene and C60 on boron nitride and graphene
• Structural and excited-state properties of oligoacene crystals from first principles
• Interpretation of van der Waals density functionals
• Desorption of n-alkanes from graphene: a van der Waals density functional study
• Finite-temperature properties of non-magnetic transition metals: Comparison of the performance of constraint-based semi and nonlocal functionals
• libvdwxc: A library for exchange-correlation functionals in the vdW-DF family
• Structure and binding in crystals of cage-like molecules: hexamine and platonic hydrocarbons

Cited by in corpus (15)

• Next-generation non-local van der Waals density functional
• Nonlocal van der Waals functionals for solids: Choosing an appropriate one
• Screening nature of the van der Waals density functional method: A review and analysis of the many-body physics foundation
• Atomic scale mechanisms controlling the oxidation of polyethylene: a first principles study
• Broken adiabaticity induced by Lifshitz transition in MoS${}_2$ and WS${}_2$ single layers
• van der Waals density functional with corrected $C_6$ coefficients
• Signatures of van der Waals binding: a coupling-constant scaling analysis
• Accurate non-empirical range-separated hybrid van der Waals density functional for complex molecular problems, solids, and surfaces
• Extent of Fock-exchange mixing for a hybrid van der Waals density functional?
• Energy scaling law for nanostructured materials
• vdW-DF-ahcx: a range-separated van der Waals density functional hybrid
• Improved proton-transfer barriers with van der Waals density functionals: Role of repulsive non-local correlation
• Interaction of water with nitrogen-doped graphene
• Phosphorene Nanoribbon Based Nano-Electrodes for Explosives Detection: A DFT Study
• A Denser Hydrogen Inferred from First-Principles Simulations Challenges Jupiter's Interior Models