Dissociative Chemisorption of O₂ on Al(111): Dynamics on a Correlated Wave-Function-Based Potential Energy Surface

Abstract

Dissociative chemisorption of O2 on the Al(111) surface represents an extensively studied prototype for understanding the interaction between O2 and metal surfaces. It is well known that the experimentally observed activation barrier for O2 dissociation is not captured by conventional density functional theory. The interpretation of this barrier as a result of spin transitions along the reaction path has been challenged by recent embedded correlated wave function (ECW) calculations that naturally yield an adiabatic barrier. However, the ECW calculations have been limited to a static analysis of the reaction pathways and have not yet been tested by dynamics simulations. We present a global six-dimensional potential energy surface (PES) for this system parametrized with ECW data points. This new PES provides a reasonable description of the site-specific and orientation-dependent activation barriers. Quasi-classical trajectory calculations on this PES semiquantitatively reproduce both the observed translational energy dependence of the sticking probability and steric effects with aligned O2 molecules.

Density Functional Theory for Molecule–Metal Surface Reactions: When Does the Generalized Gradient Approximation Get It Right, and What to Do If It Does Not

“…However, drawbacks of the ECW method are that it is expensive to use and that it is hard to converge the molecule–surface interaction energy with respect to the size of the embedded cluster. 36 Consequently, Yin et al 62 had to base their PES on a limited amount of points, which forced them to adopt a fitting method that is of only medium accuracy (i.e., a flexible periodic London–Eyring–Polanyi–Sato (FPLEPS) function 71 ) to represent their ECW data. Additionally, it is not so clear how the ECW method could be used in an SRP approach, whereas this is rather obvious for DFT.…”

“…The green line indicates results obtained with the (R)PBE DF, 24 , 43 whereas the blue and red circles indicate QCT results obtained here with the MS-RPBEl and HSE03-1/3X DFs, respectively. The black diamonds and orange squares indicate experimental results 61 and QCT results obtained with an ECW PES, 62 respectively. (b) Sticking probability of O 2 (ν = 0, J = 2, K = 1) on Al(111) for the helicopter (red downward pointing triangle), random (black circle), and perpendicular (blue upward pointing triangle) orientations.…”

Reactive and Nonreactive Scattering of HCl from Au(111): An Ab Initio Molecular Dynamics Study

“…We therefore suggest that an electronic structure method of which the accuracy is not adversely affected by charge transfer between the surface and the molecule, such as diffusion Monte-Carlo 65 or density functional embedded wave function theory, 66,67 should be used to investigate the reaction barrier height for HCl + Au(111). The latter has very recently been applied in the development of a six-dimensional PES for the O 2 + Al(111) system, 68 which has successfully captured the activated feature and steric effect that are observed experimentally but absent with GGA-DFT calculations.…”

Electronic factors determining the methane bond breaking process on small aluminum clusters

“…Whereas the interaction of oxygen with Al clusters has been studied intensively, relative few studies have been devoted to the interaction of hydrocarbons such as methane with Al clusters . This is surprising as the activation and functionalization of methane represent one of the grand challenges in modern catalysis .…”

“…[16] Recently there have been significant advances in these field, also due to developments in instrumentation and technology. [19] Whereas the interaction of oxygen with Al clusters has been studied intensively, [20][21][22][23][24][25][26][27][28] relative few studies have been devoted to the interaction of hydrocarbons such as methane with Al clusters. [19] This is surprising as the activation and functionalization of methane represent one of the grand challenges in modern catalysis.…”