Orbital-Dependent Electronic Friction Significantly Affects the Description of Reactive Scattering of N₂ from Ru(0001)

Abstract

Electron–hole pair (ehp) excitation is thought to substantially affect the dynamics of molecules on metal surfaces, but it is not clear whether this can be better addressed by orbital-dependent friction (ODF) or the local density friction approximation (LDFA). We investigate the effect of ehp excitation on the dissociative chemisorption of N2 on and its inelastic scattering from Ru(0001), which is the benchmark system of highly activated dissociation, with these two different models. ODF is in better agreement with the best experimental estimates for the reaction probabilities than LDFA, yields results for vibrational excitation in better agreement with experiment, but slightly overestimates the translational energy loss during scattering. N2 on Ru(0001) is thus the first system for which the ODF and LDFA approaches are shown to yield substantially different results for easily accessible experimental observables, including reaction probabilities.

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

“…On the other hand, the SRP DF for H 2 + Cu(111) 4 and Cu(100) 5 needs to contain about 50% RPBE exchange, and a good description of N 2 + Ru(0001) was recently obtained with the RPBE DF. 10 …”

Symmetry-Adapted High Dimensional Neural Network Representation of Electronic Friction Tensor of Adsorbates on Metals

“…35,[44][45][46][47][48] In principle, the full-rank EFT can be obtained by the first-order time-dependent perturbation theory (TDPT) based on KS orbitals of DFT that fully accounts for the electronic structure of molecule-surface system. 21 Very recently, Meyer et al [52][53] and we [54][55] have independently discussed the influence of mode specific electronic frictions on dissociative sticking and state-to-state scattering probabilities of N2 and H2 on metal surfaces, both using a neural network (NN) representation but with different approaches to describe the symmetry properties of EFT. Meyer and coworkers started from a reduced-dimensional NN representation of EFT with a fixed reference molecular orientation, followed by the multiplication with an approximate rotation matrix to obtain the six-dimensional EFT.…”

Electronic friction coefficients from the atom-in-jellium model for Z=1–92

“…Therefore, the validity of the BO approximation has been questioned for a long time [4,5]. Even though ehp excitations have been neglected in many theoretical studies in the past, which could also explain experimental data [6][7][8][9][10][11][12], recent studies indicate that ehp excitations can play an important role in the dynamics of molecule-surface reactions [13][14][15][16][17][18][19][20][21][22]. For example, vibrational lifetimes of simple diatomic molecules adsorbed on metal surfaces were only explained by going beyond the BO approximation [17,[23][24][25][26][27][28][29][30][31][32][33][34].…”

“…For going beyond the BO approximation, a commonly used approach is combining ab initio molecular dynamics with electronic friction theory [16,20]. Using the local density friction approximation (LDFA) is a way to include the dissipative effect of electron-hole pair excitations in molecular dynamics [14] that is computationally much more convenient than other approaches [21,22,[38][39][40][41]. Within the LDFA, including the independent atom approximation, the so-called electronic friction coefficient η is required.…”