The shortcomings of semi-local and hybrid functionals: what we can learn from surface science studies

A study of the adsorption of CO on late 4d and $5d$ transition metal (111) surfaces (Ru, Rh, Pd, Ag, Os, Ir, and Pt) considering atop and hollow site adsorption is presented. The applied functionals include the gradient corrected PBE and BLYP functional, and the corresponding hybrid Hartree-Fock density functionals HSE and B3LYP. We find that PBE based hybrid functionals (specifically HSE) yield, with the exception of Pt, the correct site order on all considered metals, but they also considerably overestimate the adsorption energies compared to experiment. On the other hand, the semi-local BLYP functional and the corresponding hybrid functional B3LYP yield very satisfactory adsorption energies and the correct adsorption site for all surfaces. We are thus faced with a Procrustean problem: the B3LYP and BLYP functionals seem to be the overall best choice for describing adsorption on metal surfaces, but they simultaneously fail to account well for the properties of the metal, vastly overestimating the equilibrium volume and underestimating the atomization energies. Setting out from these observations, general conclusions are drawn on the relative merits and drawbacks of various semi-local and hybrid functionals. The discussion includes a revised version of the PBE functional specifically optimized for bulk properties and surface energies (PBEsol), a revised version of the PBE functional specifically optimized to predict accurate adsorption energies (rPBE), as well as the aforementioned BLYP functional. We conclude that no semi-local functional is capable to describe all aspects properly, and including non-local exchange also only improves some, but worsens other properties.Comment: 12 pages, 6 figures; to be published in New Journal of Physic

The asymmetric exclusion process: Comparison of update procedures

The asymmetric exclusion process (ASEP) has attracted a lot of interest not only because its many applications, e.g. in the context of the kinetics of biopolymerization and traffic flow theory, but also because it is a paradigmatic model for nonequilibrium systems. Here we study the ASEP for different types of updates, namely random-sequential, sequential, sublattice-parallel and parallel. In order to compare the effects of the different update procedures on the properties of the stationary state, we use large-scale Monte Carlo simulations and analytical methods, especially the so-called matrix-product Ansatz (MPA). We present in detail the exact solution for the model with sublattice-parallel and sequential updates using the MPA. For the case of parallel update, which is important for applications like traffic flow theory, we determine the phase diagram, the current, and density profiles based on Monte Carlo simulations. We furthermore suggest a MPA for that case and derive the corresponding matrix algebra.Comment: 47 pages (11 PostScript figures included), LATEX, Two misprints in equations correcte

Disorder Effects in CA-Models for Traffic Flow

We investigate the effect of quenched disorder in the Nagel-Schreckenberg model of traffic flow. Spatial inhomogenities, i.e. lattice sites where the braking probability is enlarged, are considered as well as particle disorder, i.e. cars of a different maximum velocity. Both types of disorder lead to segregated states.Comment: 6 pages, 4 postscript figures, Proceedings of the conference "Traffic and Granular Flow '97", Duisburg, Germany, October 5-8, 199

Metastable States in Cellular Automata for Traffic Flow

Measurements on real traffic have revealed the existence of metastable states with very high flow. Such states have not been observed in the Nagel-Schreckenberg (NaSch) model which is the basic cellular automaton for the description of traffic. Here we propose a simple generalization of the NaSch model by introducing a velocity-dependent randomization. We investigate a special case which belongs to the so-called slow-to-start rules. It is shown that this model exhibits metastable states, thus sheding some light on the prerequisites for the occurance of hysteresis effects in the flow-density relation.Comment: 15 pages, 8 ps-figures included; accepted for publication in EPJ

Particle interactions and lattice dynamics: Scenarios for efficient bidirectional stochastic transport?

Intracellular transport processes driven by molecular motors can be described by stochastic lattice models of self-driven particles. Here we focus on bidirectional transport models excluding the exchange of particles on the same track. We explore the possibility to have efficient transport in these systems. One possibility would be to have appropriate interactions between the various motors' species, so as to form lanes. However, we show that the lane formation mechanism based on modified attachment/detachment rates as it was proposed previously is not necessarily connected to an efficient transport state and is suppressed when the diffusivity of unbound particles is finite. We propose another interaction mechanism based on obstacle avoidance that allows to have lane formation for limited diffusion. Besides, we had shown in a separate paper that the dynamics of the lattice itself could be a key ingredient for the efficiency of bidirectional transport. Here we show that lattice dynamics and interactions can both contribute in a cooperative way to the efficiency of transport. In particular, lattice dynamics can decrease the interaction threshold beyond which lanes form. Lattice dynamics may also enhance the transport capacity of the system even when lane formation is suppressed.Comment: 25 pages, 17 figures, 2 table