Assessment of density functional methods with correct asymptotic behavior

Abstract

Long-range corrected (LC) hybrid functionals and asymptotically corrected (AC) model potentials are two distinct density functional methods with correct asymptotic behavior. They are known to be accurate for properties that are sensitive to the asymptote of the exchange-correlation potential, such as the highest occupied molecular orbital energies and Rydberg excitation energies of molecules. To provide a comprehensive comparison, we investigate the performance of the two schemes and others on a very wide range of applications, including the asymptote problems, self-interaction-error problems, energy-gap problems, charge-transfer problems, and many others. The LC hybrid scheme is shown to consistently outperform the AC model potential scheme. In addition, to be consistent with the molecules collected in the IP131 database [Y.-S. Lin, C.-W. Tsai, G.-D. Li, and J.-D. Chai, J. Chem. Phys., 2012, 136, 154109], we expand the EA115 and FG115 databases to include, respectively, the vertical electron affinities and fundamental gaps of the additional 16 molecules, and develop a new database AE113 (113 atomization energies), consisting of accurate reference values for the atomization energies of the 113 molecules in IP131. These databases will be useful for assessing the accuracy of density functional methods.

accepted for publication in Phys. Chem. Chem. Phys., 46 pages, 4 figures, supplementary material included

References in corpus (7)

• Long-Range Corrected Hybrid Density Functionals with Improved Dispersion Corrections
• Fractional charge perspective on the band-gap in density-functional theory
• The discontinuous nature of the exchange-correlation functional -- critical for strongly correlated systems
• Density functional theory with fractional orbital occupations
• Long-range corrected hybrid meta-generalized-gradient approximations with dispersion corrections
• Discontinuities of the exchange-correlation kernel and charge-transfer excitations in time-dependent density functional theory
• Restoration of the Derivative Discontinuity in Kohn-Sham Density Functional Theory: An Efficient Scheme for Energy Gap Correction

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• Asymptotic Correction Schemes for Semilocal Exchange-Correlation Functionals
• Employing Range Separation on the meta-GGA Rung: New Functional Suitable for Both Covalent and Noncovalent Interactions
• Van der Waals interactions in rare-gas dimers: The role of interparticle interactions
• Assessment of asymptotically corrected model potential scheme for charge-transfer-like excitations in oligoacenes
• Assessment of the LFAs-PBE exchange-correlation potential for high-order harmonic generation of aligned H2+ molecules