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

Why is a noble metal catalytically active? The role of the O-Ag interaction in the function of silver as an oxidation catalyst

Extensive density-functional theory calculations, and taking into account temperature and pressure, affords a comprehensive picture of the behavior and interaction of oxygen and Ag(111), and provides valuable insight into the function of silver as an oxidation catalyst. The obtained phase-diagram reveals the most stable species present in a given environment and thus identifies (and excludes) possibly active oxygen species. In particular, for the conditions of ethylene epoxidation, a thin oxide-like structure is most stable, suggesting that such atomic O species are actuating the catalysis, in contrast to hitherto proposed molecular-like species.Comment: 4 pages including 3 figures, Related publications can be found at http://www.fhi-berlin.mpg.de/th/paper.htm

Evaluation of Herbicide Efficacy, Injury, and Yield in White Lupin (Lupinus albus L.)

White lupin is of increasing interest in the southeastern United States (US) as a winter legume cover crop or as mid-winter forage for ruminants. White lupins are poor weed competitors during early establishment, making effective weed control necessary; however, only three herbicides are currently registered for use in lupin. An experiment was conducted at two Alabama sites in 2007 and 2008 to evaluate herbicide efficacy provided by ten preemergence (PRE) and nine postemergence (POST) herbicides as well as lupin injury and yield. Overall, PRE applied herbicides, particularly imazethapyr, linuron, and flumioxazin, caused less crop injury than POST herbicides while providing ≥ 86% control of annual bluegrass, corn spurry, heartwing sorrel, henbit, and lesser swinecress six weeks after application. Grass-active herbicides, fluazifop and sethoxydim, provided greater than 95% of annual bluegrass control without causing unrecoverable lupin damage. Imazethapyr applied POST controlled shepherd’s purse (96% to 98%), cutleaf evening-primrose (81% to 96%), and wild radish (71% to 99%) without lupin injury. POST-directed spray applications of glyphosate and flumioxazin provided good weed control of corn spurry (80% to 98%) and winter vetch (71% to 95%) but caused significant crop injury due to drift. In general, grain yields were only reduced with the use of chlorimuron, diclosulam, glyphosate, and thifensulfuron. This research suggests there are several herbicides not currently registered that could be beneficial for use in US lupin production

Frozen thermal fluctuations in adsorbate-induced step restructuring

Ammonia adsorbed on a Pt(443) surface causes meandering of the initially straight edges at 300 K. Based on density-functional theory calculations and on kinetic Monte Carlo simulations it is shown that the meandering is not an equilibrium structure stabilized by the larger adsorption energy of ammonia at step and kink sites. Rather the meandering has to be interpreted as a frozen thermal fluctuation caused by ammonia which strongly reduces the stiffness of the step edges at intermediate ammonia coverages