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

Effect of on- and off-ramps in cellular automata models for traffic flow

We present results on the modeling of on- and off-ramps in cellular automata for traffic flow, especially the Nagel-Schreckenberg model. We study two different types of on-ramps that cause qualitatively the same effects. In a certain density regime one observes plateau formation in the fundamental diagram. The plateau value depends on the input-rate of cars at the on-ramp. The on-ramp acts as a local perturbation that separates the system into two regimes: A regime of free flow and another one where only jammed states exist. This phase separation is the reason for the plateau formation and implies a behaviour analogous to that of stationary defects. This analogy allows to perform very fast simulations of complex traffic networks with a large number of on- and off-ramps because one can parametrise on-ramps in an exceedingly easy way.Comment: 11 pages, 9 figures, accepted for publication in Int. J. Mod. Phys.

Boundary-induced phase transitions in traffic flow

Boundary-induced phase transitions are one of the surprising phenomena appearing in nonequilibrium systems. These transitions have been found in driven systems, especially the asymmetric simple exclusion process. However, so far no direct observations of this phenomenon in real systems exists. Here we present evidence for the appearance of such a nonequilibrium phase transition in traffic flow occurring on highways in the vicinity of on- and off-ramps. Measurements on a German motorway close to Cologne show a first-order nonequilibrium phase transition between a free-flow phase and a congested phase. It is induced by the interplay of density waves (caused by an on-ramp) and a shock wave moving on the motorway. The full phase diagram, including the effect of off-ramps, is explored using computer simulations and suggests means to optimize the capacity of a traffic network.Comment: 5 figures, revte

A model for bidirectional traffic of cytoskeletal motors

We introduce a stochastic lattice gas model including two particle species and two parallel lanes. One lane with exclusion interaction and directed motion and the other lane without exclusion and unbiased diffusion, mimicking a micotubule filament and the surrounding solution. For a high binding affinity to the filament, jam-like situations dominate the system's behaviour. The fundamental process of position exchange of two particles is approximated. In the case of a many-particle system, we were able to identify a regime in which the system is rather homogenous presenting only small accumulations of particles and a regime in which an important fraction of all particles accumulates in the same cluster. Numerical data proposes that this cluster formation will occur at all densities for large system sizes. Coupling of several filaments leads to an enhanced cluster formation compared to the uncoupled system, suggesting that efficient bidirectional transport on one-dimensional filaments relies on long-ranged interactions and track formation.Comment: 20 pages, 9 figure

Modeling the sorption dynamics of NaH using a reactive force field

We have parametrized a reactive force field for NaH, ReaxFFNaH, against a training set of ab initio derived data. To ascertain that ReaxFFNaH is properly parametrized, a comparison between ab initio heats of formation of small representative NaH clusters with ReaxFFNaH was done. The results and trend of ReaxFFNaH are found to be consistent with ab initio values. Further validation includes comparing the equations of state of condensed phases of Na and NaH as calculated from ab initio and ReaxFFNaH. There is a good match between the two results, showing that ReaxFFNaH is correctly parametrized by the ab initio training set. ReaxFFNaH has been used to study the dynamics of hydrogen desorption in NaH particles. We find that ReaxFFNaH properly describes the surface molecular hydrogen charge transfer during the abstraction process. Results on heat of desorption versus cluster size shows that there is a strong dependence on the heat of desorption on the particle size, which implies that nanostructuring enhances desorption process. To gain more insight into the structural transformations of NaH during thermal decomposition, we performed a heating run in a molecular dynamics simulation. These runs exhibit a series of drops in potential energy, associated with cluster fragmentation and desorption of molecular hydrogen. This is consistent with experimental evidence that NaH dissociates at its melting point into smaller fragments

Parametrization of a reactive force field for aluminum hydride

A reactive force field, REAXFF, for aluminum hydride has been developed based on density functional theory (DFT) derived data. REAXFF_(AlH_3) is used to study the dynamics governing hydrogen desorption in AlH_3. During the abstraction process of surface molecular hydrogen charge transfer is found to be well described by REAXFF_(AlH_3). Results on heat of desorption versus cluster size show that there is a strong dependence of the heat of desorption on the particle size, which implies that nanostructuring enhances desorption process. In the gas phase, it was observed that small alane clusters agglomerated into a bigger cluster. After agglomeration molecular hydrogen was desorbed from the structure. This thermodynamically driven spontaneous agglomeration followed by desorption of molecular hydrogen provides a mechanism on how mobile alane clusters can facilitate the mass transport of aluminum atoms during the thermal decomposition of NaAlH_4

Predictions of melting, crystallization, and local atomic arrangements of aluminum clusters using a reactive force field

A parametrized reactive force field model for aluminum ReaxFFAl has been developed based on density functional theory (DFT) data. A comparison has been made between DFT and ReaxFFAl outputs to ascertain whether ReaxFFAl is properly parametrized and to check if the output of the latter has correlation with DFT results. Further checks include comparing the equations of state of condensed phases of Al as calculated from DFT and ReaxFFAl. There is a good match between the two results, again showing that ReaxFFAl is correctly parametrized as per the DFT input. Simulated annealing has been performed on aluminum clusters Aln using ReaxFFAl to find the stable isomers of the clusters. A plot of stability function versus cluster size shows the existence of highly stable clusters (magic clusters). Quantum mechanically these magic clusters arise due to the complete filling of the orbital shells. However, since force fields do not care about electrons but work on the assumption of validity of Born–Oppenheimer approximation, the magic clusters are therefore correlated with high structural symmetry. There is a rapid decline in surface energy contribution due to the triangulated nature of the surface atoms leading to higher coordination number. The bulk binding energy is computed to be 76.8 kcal/mol. This gives confidence in the suitability of ReaxFF for studying and understanding the underlying dynamics in aluminum clusters. In the quantification of the growth of cluster it is seen that as the size of the clusters increase there is preference for the coexistence of fcc/hcp orders at the expense of simple icosahedral ordering, although there is some contribution from distorted icosahedral ordering. It is found that even for aluminum clusters with 512 atoms distorted icosahedral ordering exists. For clusters with N≥256 atoms fcc ordering dominates, which implies that at this point we are already on the threshold of bulklike bonding

Partially asymmetric exclusion models with quenched disorder

We consider the one-dimensional partially asymmetric exclusion process with random hopping rates, in which a fraction of particles (or sites) have a preferential jumping direction against the global drift. In this case the accumulated distance traveled by the particles, x, scales with the time, t, as x ~ t^{1/z}, with a dynamical exponent z > 0. Using extreme value statistics and an asymptotically exact strong disorder renormalization group method we analytically calculate, z_{pt}, for particlewise (pt) disorder, which is argued to be related to the dynamical exponent for sitewise (st) disorder as z_{st}=z_{pt}/2. In the symmetric situation with zero mean drift the particle diffusion is ultra-slow, logarithmic in time.Comment: 4 pages, 3 figure

Asymmetric simple exclusion process in one-dimensional chains with long-range links

We study the boundary-driven asymmetric simple exclusion process (ASEP) in a one-dimensional chain with long-range links. Shortcuts are added to a chain by connecting $pL$ different pairs of sites selected randomly where $L$ and $p$ denote the chain length and the shortcut density, respectively. Particles flow into a chain at one boundary at rate $\alpha$ and out of a chain at the other boundary at rate $\beta$, while they hop inside a chain via nearest-neighbor bonds and long-range shortcuts. Without shortcuts, the model reduces to the boundary-driven ASEP in a one-dimensional chain which displays the low density, high density, and maximal current phases. Shortcuts lead to a drastic change. Numerical simulation studies suggest that there emerge three phases; an empty phase with $\rho = 0$, a jammed phase with $\rho = 1$, and a shock phase with $0<\rho<1$ where $\rho$ is the mean particle density. The shock phase is characterized with a phase separation between an empty region and a jammed region with a localized shock between them. The mechanism for the shock formation and the non-equilibrium phase transition is explained by an analytic theory based on a mean-field approximation and an annealed approximation.Comment: revised version (16 pages and 6 eps figures