Analytical representation of the Becke-Roussel exchange functional.
نویسندگان
چکیده
The unique meta-GGA (generalized gradient approximation) exchange functional of Becke and Roussel (BR89) and the correlation functional of Becke related to it (B94) are represented for the first time in an analytical form. All functional derivatives are then obtained analytically, which allows an efficient self-consistent implementation. A brief assessment of this "BR89B94" meta-GGA scheme is made considering molecular atomization energies and equilibrium geometries, with the latter being reported for the first time. The hybrid version of it yields one of the most accurate atomization energies to date, but its bond distances are less satisfactory. Some interesting features of the BR exchange hole are discussed.
منابع مشابه
How Close Are the Slater and Becke–Roussel Potentials in Solids?
The Becke–Roussel (BR) potential [Phys. Rev. A 1989, 39, 3761] was proposed as an approximation to the Slater potential, which is the Coulomb potential generated by the exact exchange hole. In the present work, a detailed comparison between the Slater and BR potentials in solids is presented. It is shown that the two potentials usually lead to very similar results for the electronic structure; ...
متن کاملCharge density reconstitution from approximate exchange-correlation holes
The electronic charge density and the expectation of any monoelectronic operator can be reconstructed by a density-weighted integral of the exchange-correlation hole. This property can be used to test and improve approximate holes that are not spherically averaged. As an example, we test the Becke–Roussel exhange-hole model in its nonspherical formulation on small atoms, finding that it accurat...
متن کاملNon-empirical derivation of the parameter in the B88 exchange functional
The B88 exchange energy density functional (created by Becke in 1988) is a crucial part of the most popular density functional in use today, B3LYP. B88 contains one empirical parameter which was fitted to Hartree–Fock exchange energies for the noble gas atoms. We show how local approximations to exchange become relatively exact under a very specific approach to the limit of large numbers, but t...
متن کاملFunctional Theory to the Structures and Thermochemistries of ScF 3 , TiF 4 , VF 5 , and CrF 6
Density functional theory(DFT) and Hartree-Fock(HF) calculations are reported for the family of transition metal fluorides ScF3, TiF4, VF5, and CrF6. Both HF and the local-density-aproximation (LDA) yield excellent agreement with experimental bond lengths, while the B-LYP gradient-corrected density functional gives bond lengths 0.04 − 0.05 Å too long. An investigation of various combinations of...
متن کاملAn Investigation of the Performance of a Hybrid of Hartree-Fock and Density Functional Theory
We explore a hybrid methodology in which the Hartree-Fock energy and density are combined with the nonlocal exchange functional of Becke ( 1988) and the nonlocal correlation functional of Lee, Yang and Pam ( 1988) to yield an estimate of the Schriidinger total energy. The resulting mean absolute deviation from a large number of experimental atomization energies, ionization potentials, electron ...
متن کاملذخیره در منابع من
با ذخیره ی این منبع در منابع من، دسترسی به آن را برای استفاده های بعدی آسان تر کنید
برای دانلود متن کامل این مقاله و بیش از 32 میلیون مقاله دیگر ابتدا ثبت نام کنید
ثبت ناماگر عضو سایت هستید لطفا وارد حساب کاربری خود شوید
ورودعنوان ژورنال:
- Chemical physics letters
دوره 455 1-3 شماره
صفحات -
تاریخ انتشار 2008