Atoms, molecules, solids, and surfaces: Applications of the generalized gradient approximation for exchange and correlation.
John P. Perdew,J. A. Chevary,S. H. Vosko,Koblar A. Jackson,Mark R. Pederson,David J. Singh,Carlos Fiolhais +6 more
TLDR
A way is found to visualize and understand the nonlocality of exchange and correlation, its origins, and its physical effects as well as significant interconfigurational and interterm errors remain.Abstract:
Generalized gradient approximations (GGA's) seek to improve upon the accuracy of the local-spin-density (LSD) approximation in electronic-structure calculations. Perdew and Wang have developed a GGA based on real-space cutoff of the spurious long-range components of the second-order gradient expansion for the exchange-correlation hole. We have found that this density functional performs well in numerical tests for a variety of systems: (1) Total energies of 30 atoms are highly accurate. (2) Ionization energies and electron affinities are improved in a statistical sense, although significant interconfigurational and interterm errors remain. (3) Accurate atomization energies are found for seven hydrocarbon molecules, with a rms error per bond of 0.1 eV, compared with 0.7 eV for the LSD approximation and 2.4 eV for the Hartree-Fock approximation. (4) For atoms and molecules, there is a cancellation of error between density functionals for exchange and correlation, which is most striking whenever the Hartree-Fock result is furthest from experiment. (5) The surprising LSD underestimation of the lattice constants of Li and Na by 3--4 % is corrected, and the magnetic ground state of solid Fe is restored. (6) The work function, surface energy (neglecting the long-range contribution), and curvature energy of a metallic surface are all slightly reduced in comparison with LSD. Taking account of the positive long-range contribution, we find surface and curvature energies in good agreement with experimental or exact values. Finally, a way is found to visualize and understand the nonlocality of exchange and correlation, its origins, and its physical effects.read more
Citations
More filters
Journal ArticleDOI
WIEN2k: An APW+lo program for calculating the properties of solids
Peter Blaha,Karlheinz Schwarz,Fabien Tran,Robert Laskowski,Georg K. H. Madsen,Laurence D. Marks +5 more
TL;DR: The WIEN2k program is based on the augmented plane wave plus local orbitals (APW+lo) method to solve the Kohn-Sham equations of density functional theory, and the various options, properties, and available approximations for the exchange-correlation functional are mentioned.
Journal ArticleDOI
Orbital-dependent density functionals: Theory and applications
Stephan Kümmel,Leeor Kronik +1 more
TL;DR: In this article, the authors provide a perspective on the use of orbital-dependent functionals, which is currently considered one of the most promising avenues in modern density-functional theory.
Journal ArticleDOI
Alloy catalysts designed from first principles
Jeffrey Greeley,Manos Mavrikakis +1 more
TL;DR: Density functional theory calculations are used to introduce a new class of near-surface alloys that can yield superior catalytic behaviour for hydrogen-related reactions and may permit these alloys to serve as low-temperature, highly selective catalysts for pharmaceuticals production and as robust fuel-cell anodes.
Journal ArticleDOI
Steam Reforming and Graphite Formation on Ni Catalysts
Hanne Skov Bengaard,Jens K. Nørskov,Jens Sehested,Clausen Bjerne Steffen,L.P. Nielsen,A.M. Molenbroek,Jens R. Rostrup-Nielsen +6 more
TL;DR: Based on density functional theory calculations, kinetic measurements, microkinetic and Monte Carlo simulations, thermogravimetric analysis (TGA) experiments, extended X-ray absorption spectroscopy (EXAFS) measurements, and experimental results from the literature, this paper presented a detailed and comprehensive mechanistic picture of the steam reforming process on a Ni catalyst.
Journal ArticleDOI
Hydrogen bonding and stacking interactions of nucleic acid base pairs: A density-functional-theory based treatment
TL;DR: In this article, an empirical formula consisting of an R−6 term is introduced, which is appropriately damped for short distances; the corresponding C6 coefficient, calculated from experimental atomic polarizabilities, can be consistently added to the total energy expression.
Related Papers (5)
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set.
Georg Kresse,Jürgen Furthmüller +1 more