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
Organocalcium-mediated nucleophilic alkylation of benzene
TL;DR: Several organocalcium compounds prepared can alkylate benzene by displacing a hydride, with no need for a more conventionally reactive leaving group such as chloride (see the Perspective by Mulvey).
Journal ArticleDOI
Perspectives on the first principles elucidation and the design of active sites
TL;DR: In this article, an ab initio-based kinetic Monte Carlo simulation scheme was developed and used to engineer Pd/Au alloys in order to improve the activity for vinyl acetate synthesis by about a factor of 2 and the selectivity by about 5%.
Journal ArticleDOI
Temperature-Sensitive Structure Evolution of Lithium–Manganese-Rich Layered Oxides for Lithium-Ion Batteries
Haijun Yu,Yeong-Gi So,Yang Ren,Tianhao Wu,Gencai Guo,Ruijuan Xiao,Jun Lu,Hong Li,Yubo Yang,Haoshen Zhou,Ru-Zhi Wang,Khalil Amine,Yuichi Ikuhara +12 more
TL;DR: This study clarifies the structural evolution mechanism of these lithium-rich layered oxides and opens the door to the design of similar high-energy materials with better cycle stability.
Journal ArticleDOI
Structural, spectroscopic, and redox consequences of a central ligand in the FeMoco of nitrogenase: a density functional theoretical study.
TL;DR: The calculated structural, spectroscopic, and redox data indicate the most likely iron oxidation state for the resting FeMoco of nitrogenase to be 4Fe(2+)3Fe(3+).
Journal ArticleDOI
Sulfur bonding in MoS2 and Co-Mo-S structures
TL;DR: In this paper, the structure and bonding in small MoS2 structures with and without Co are studied theoretically using self-consistent density functional theory with a non-local exchange-correlation energy.
Related Papers (5)
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set.
Georg Kresse,Jürgen Furthmüller +1 more