Nonuniversality of commonly used correlation-energy density functionals.
نویسندگان
چکیده
The correlation energies of the helium isoelectronic sequence and of Hooke's atom isoelectronic sequence have been evaluated using an assortment of local, gradient, and metagradient density functionals. The results are compared with the exact correlation energies, showing that while several of the more recent density functionals reproduce the exact correlation energies of the helium isoelectronic sequence rather closely, none is satisfactory for Hooke's atom isoelectronic sequence. It is argued that the uniformly acceptable results for the helium sequence can be explained through simple scaling arguments that do not hold for Hooke's atom sequence, so that the latter system provides a more sensitive testing ground for approximate density functionals. This state of affairs calls for further effort towards formulating correlation-energy density functionals that would be truly universal at least for spherically symmetric two-fermion systems.
منابع مشابه
Ground-state energies of isoelectronic atomic series from density-functional theory: Exploring the accuracy of density functionals
The performance of commonly used correlation and exchange-correlation functionals has been studied for highly charged atomic ions. Calculated energies have been compared with exact nonrelativistic energies of atomic species with 2–18 electrons for nuclei from Z 2 He to Z 26 Ni . It is found that all density functionals considered here reveal problems in the description of correlation effects as...
متن کاملFirst–Principle Calculation of the Electronic and Optical Properties of Nanolayered ZnO Polymorphs by PBE and mBJ Density Functionals
First principle calculations of nanolayered ZnO polymorphs (Wurzite–, Zincblende–, Rocksalt–structures) in the scheme of density functional theory were performedwith the help of full potential linear augmented plane wave (FP-LAPW) method. Theexchange - correlation potential is described by generalized gradient approximation asproposed by Perdew–Burke–Ernzrhof (GGA–PBE) and modified Becke–Johns...
متن کاملGradient corrections to the exchange-correlation free energy
We develop the first-order gradient correction to the exchange-correlation free energy of the homogeneous electron gas for use in finite-temperature density functional calculations. Based on this, we propose and implement a simple temperature-dependent extension for functionals beyond the local density approximation. These finitetemperature functionals show improvement over zero-temperature fun...
متن کاملDispersion Correction Derived from First Principles for Density Functional Theory and Hartreeâ‹TMFock Theory
The modeling of dispersion interactions in density functional theory (DFT) is commonly performed using an energy correction that involves empirically fitted parameters for all atom pairs of the system investigated. In this study, the first-principles-derived dispersion energy from the effective fragment potential (EFP) method is implemented for the density functional theory (DFT-D(EFP)) and Har...
متن کاملGeneralized gradient approximations to density functional theory: comparison with exact results
In order to assess the accuracy of commonly used approximate exchange-correlation density functionals, we present a comparison of accurate exchange and correlation potentials, exchange energy densities and energy components with the corresponding approximate quantities. Four systems are used as illustrative examples: the model system of two electrons in a harmonic potential and the He, Be and N...
متن کاملذخیره در منابع من
با ذخیره ی این منبع در منابع من، دسترسی به آن را برای استفاده های بعدی آسان تر کنید
عنوان ژورنال:
- The Journal of chemical physics
دوره 124 23 شماره
صفحات -
تاریخ انتشار 2006