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
Combining multideterminantal wave functions with density functionals to handle near-degeneracy in atoms and molecules
TL;DR: In this paper, an economical method that mixes configuration interaction (CI) and density functional theory (DFT) is proposed to control near-degeneracy effects and dynamical correlation in atoms and molecules.
Journal ArticleDOI
Atomistic modeling of an Fe system with a small concentration of C
Charlotte Becquart,Jean-Marc Raulot,Guy Bencteux,Christophe Domain,Michel Perez,Sébastien Garruchet,Hoang Nguyen +6 more
TL;DR: In this article, an embedded atom method has been used to derive an Fe-C potential, adjusted on ab initio data, dedicated to the study of ferritic FeC solid solutions for low carbon concentrations.
Journal ArticleDOI
Atmospheric effects on the adhesion and friction between non-hydrogenated diamond-like carbon (DLC) coating and aluminum – A first principles investigation
TL;DR: In this article, Density functional theory (DFT) calculations were performed to investigate the interaction of diamond surface, to represent non-hydrogenated DLC, with N2, H2, and H2O molecules.
Journal ArticleDOI
Electron transport through molecular junctions
TL;DR: In this paper, the authors give an overview of theoretical methods used to analyze the transport properties of metal-molecular junctions as well as some relevant experiments and applications and introduce a Hamiltonian which can be used to analyse electron-electron, electron-phonon and spin-orbit interactions.
Related Papers (5)
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set.
Georg Kresse,Jürgen Furthmüller +1 more