An improved static corrugation model

Abstract

Accurately describing surface temperature effects for the dissociation of H 2 on Cu(111) remains challenging. While Ab initio Molecular Dynamics (AIMD), the current state-of-the-art method for modelling such systems, can produce accurate results, it is computationally very expensive to use for extensive testing of, for example, density functionals. A chemically accurate static corrugation model for H 2 and D 2 on Cu(111) dissociation was made by introducing effective three-body interactions as well as an H 2 -bond dependence and fitting the model to density functional theory energies for 15 113 different configurations. Reaction probabilities and rovibrational (in)elastic scattering probabilities were computed and compared to experiments and other calculations. Theoretical and experimental results are in good agreement, except for the reaction of (v = 0, J = 0) H 2 where both AIMD and the newly developed static corrugation model, both based on the same underlying density functional, predict a similar deviation from the experiment. Published by AIP Publishing.

Quantum Dynamics of Dissociative Chemisorption of H2 on the Stepped Cu(211) Surface

“…We should also note here that when low surface temperature experiments are considered, as with the 120 K surface temperature here, it is known from the literature that the BOSS model works well for activated H 2 dissociation on metals. 26,33,34,36,60…”

“…30 All our calculations have been carried out using the BOSS model, which works well for activated H 2 dissociation on metals at low surface temperatures. 26,33−36,60…”

Designing new SRP density functionals including non-local vdW-DF2 correlation for H2 + Cu(111) and their transferability to H2 + Ag(111), Au(111) and Pt(111)

“…We choose this definition since our calculations are carried out using the BOSS model. From the literature it is known that the BOSS model works rather well for activated H 2 dissociation on cold metals 23,[27][28][29]62,147 .…”

“…The theoretical results shown here were obtained using the BOSS model. The experiments of Michelsen et al 45 and Rettner et al 53 considered here employed a low surface temperature of 120K, the experiment of Berger et al 46 was reportedly done on a 'cold' surface, and from the literature it is known that the BOSS model works well for activated H 2 dissociation on cold metals 23,[26][27][28][29] . Another advantage of fitting a SRP-DF to these sets of molecular beam experiments is that they cover both H 2 and D 2 for very different experimental conditions with respect to the nozzle temperature, the average collision energy, and the width of the velocity distributions 10 .…”

“…For this system we can have the most confidence that discrepancies between theory and experiment can be attributed to either shortcomings in DF design or the limitations of using the Born-Oppenheimer static surface (BOSS) model. It is well known that the BOSS model works well for activated H 2 dissociation on cold metals 23,[27][28][29]62 . Additionally we evaluate the performance of a SRP-DF that was fitted to the H 2 + Pt(111) system 11 for the H 2 + Cu(111) system.…”