Away from generalized gradient approximation: Orbital-dependent exchange-correlation functionals

Abstract

Rotational effects in the dissociative adsorption of H 2 on the Pt͑211͒ stepped surface have been studied using classical trajectory calculations on a six-dimensional, density-functional theory potential-energy surface. Reaction of rotating molecules via an indirect trapping mechanism exhibits an unexpected nonmonotonic dependence on the initial rotational quantum number J. Indirect reaction is first quenched with increasing J but is enhanced again for high J initial states. The quenching is attributed to rotational-to-translational energy transfer, which facilitates escape from the chemisorption wells responsible for molecular trapping. For high J, rotational and translational motions decouple, and the energy transfer is no longer possible, which leads again to trapping. Degeneracy-resolved calculations show that for high initial J, molecules rotating in a "cartwheel" fashion ͑m J =0͒ are more likely to become trapped and react indirectly than "helicoptering" molecules ͑m J = J͒. Experimental confirmation of this finding would lend strong support to the existence of the chemisorption wells that trap molecules prior to reaction.

Random-phase-approximation-based correlation energy functionals: Benchmark results for atoms

“…23, 24 Current interest in the RPA is stimulated by the concept of orbital-dependent (implicit) XC functionals, in which the XC energy is represented in terms of the KS orbitals and eigenenergies. 25,26,27,28,29 Within this approach an RPA-type correlation energy functional is most easily formulated on the basis of the KS response function. Compared to LDA/GGA-type explicit XC functionals, implicit functionals have several attractive features: (1) the exchange can be treated exactly, leading to exchange energies and potentials which are free of self-interaction; 30 (2) the long-range dispersion interaction can be correctly described; 1,17,31,32 (3) static correlation effects can be incorporated even within a spin-unpolarized formalism.…”

Comparison of theoretical and experimental dielectric functions: Electron energy-loss spectroscopy and density-functional calculations on skutterudites

“…[16][17][18] This is a very active field of research, and a number of possible solutions are emerging. [19][20][21][22][23] However, these are still usually accessible only for very small systems.…”

Self-consistent generalized Kohn-Sham local hybrid functionals of screened exchange: Combining local and range-separated hybridization

“…3 Mixing HF exchange and semilocal DFT exchange is formally justified by adiabatic connection arguments 3,4 and is thought to simulate some nondynamical correlation effects. [5][6][7][8][9][10][11][12] where semilocal exchange is exact͒. It incorporates 100% HF exchange in one-electron regions where HF exchange is the exact XC functional.…”