Density functionals with asymptotic-potential corrections are required for the simulation of spectroscopic properties of materials

Abstract

Five effects of correction of the asymptotic potential error in density functionals are identified that significantly improve calculated properties of molecular excited states involving charge-transfer character. Newly developed materials-science computational methods are used to demonstrate how these effects manifest in materials spectroscopy. Connection is made considering chlorophyll-a as a paradigm for molecular spectroscopy, 22 iconic materials as paradigms for 3D materials spectroscopy, and the VN- defect in hexagonal boron nitride as an example of the spectroscopy of defects in 2D materials pertaining to nanophotonics. Defects can equally be thought of as being "molecular" and "materials" in nature and hence bridge the realms of molecular and materials spectroscopies. It is concluded that the density functional HSE06, currently considered as the standard for accurate calculations of materials spectroscopy, should be replaced, in most instances, by the computationally similar but asymptotically corrected CAM-B3LYP functional, with some specific functionals for materials use only providing further improvements.

References in corpus (22)

• Two-Dimensional Material Nanophotonics
• Dielectric screening in two-dimensional insulators: Implications for excitonic and impurity states in graphane
• Room Temperature Initialisation and Readout of Intrinsic Spin Defects in a Van der Waals Crystal
• Identifying Carbon as the Source of Visible Single Photon Emission from Hexagonal Boron Nitride
• Photon-mediated interactions between quantum emitters in a diamond nanocavity
• Color centers in hexagonal boron nitride monolayers: A group theory and ab-initio analysis
• Quantum network nodes based on diamond qubits with an efficient nanophotonic interface
• Defect states in hexagonal boron nitride: Assignments of observed properties and prediction of properties relevant to quantum computation
• Single photon emitters in hexagonal boron nitride: A review of progress
• Nonempirical Range-separated Hybrid Functionals for Solids and Molecules
• Band gaps of crystalline solids from Wannier-localization based optimal tuning of a screened range-separated hybrid functional
• Photoluminescence and photochemistry of the $V_B^{-}$ defect in hexagonal boron nitride
• Accurate prediction of the properties of materials using the CAM-B3LYP Density Functional
• Understanding and calibrating Density-Functional-Theory calculations describing the energy and spectroscopy of defect sites in hexagonal boron nitride
• Deorbitalized meta-GGA Exchange-Correlation Functionals in Solids
• Assessing model-dielectric-dependent hybrid functionals on the antiferromagnetic transition-metal monoxides MnO, FeO, CoO, and NiO
• Orbital-free approximations to the kinetic-energy density in exchange-correlation MGGA functionals: tests on solids
• Possible nanophotonics applications of the $V_N{N}_B$ defect in hexagonal boron nitride
• Convergence of defect energetics calculations
• Excitonic properties of F-centers in $\alpha$-alumina from First Principles Calculation
• Dynamical Jahn-Teller effect in the first excited C${}_{60}^{-}$
• DMRG on top of plane-wave Kohn-Sham orbitals: case study of defected boron nitride

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