Mode Specific Electronic Friction in Dissociative Chemisorption on Metal Surfaces: H2 on Ag(111)

Abstract

(2017) Mode specific electronic friction in dissociative chemisorption on metal surfaces : H2 on Ag(111). Physical Review Letters, 118. 256001. Permanent WRAP URL:http://wrap.warwick.ac.uk/96012 Copyright and reuse:The Warwick Research Archive Portal (WRAP) makes this work by researchers of the University of Warwick available open access under the following conditions. Copyright © and all moral rights to the version of the paper presented here belong to the individual author(s) and/or other copyright owners. To the extent reasonable and practicable the material made available in WRAP has been checked for eligibility before being made available.Copies of full items can be used for personal research or study, educational, or not-for-profit purposes without prior permission or charge. Provided that the authors, title and full bibliographic details are credited, a hyperlink and/or URL is given for the original metadata page and the content is not changed in any way. Publisher statement: © 2017 American Physical Society A note on versions:The version presented here may differ from the published version or, version of record, if you wish to cite this item you are advised to consult the publisher's version. Please see the 'permanent WRAP URL' above for details on accessing the published version and note that access may require a subscription. Electronic friction and the ensuing nonadiabatic energy loss play an important role in chemical reaction dynamics at metal surfaces. Using molecular dynamics with electronic friction evaluated on-the-fly from Density Functional Theory, we find strong mode dependence and a dominance of nonadiabatic energy loss along the bond stretch coordinate for scattering and dissociative chemisorption of H2 on the Ag(111) surface. Exemplary trajectories with varying initial conditions indicate that this mode-specificity translates into modulated energy loss during a dissociative chemisorption event. Despite minor nonadiabatic energy loss of about 5%, the directionality of friction forces induces dynamical steering that affects individual reaction outcomes, specifically for low-incidence energies and vibrationally excited molecules. Mode-specific friction induces enhanced loss of rovibrational rather than translational energy and will be most visible in its effect on final energy distributions in molecular scattering experiments.

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

“…2c-d Next, we compare two representative MDEF trajectories in Fig. 3 that have been run with the same initial conditions but using EFTs calculated on-the-fly (referred to AIMD), 50 or interpolated by SNN 54 and EANN methods, respectively. As reported in previous work, 54 in previous studies, 54 except that the SNN fitted EFTs are replaced with the EANN ones.…”

“…18,[42][43] Despite these successes, LDFA has been continuously questioned in describing non-adiabatic interactions between molecules and metal surfaces, because the atomic friction coefficients intrinsically lack the directional dependence and molecular anisotropy that arises from the electron-nuclear coupling of a many-electron system described in a realistic potential. 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.…”

Semi-classical generalized Langevin equation for equilibrium and nonequilibrium molecular dynamics simulation

“…The tensorial feature of Γ e matrix in Eq. (17) was emphasized in recent works [50,51]. The off-diagonal elements of Γ e in the mode space couple different modes together and influence the energy distribution within different vibrational modes.…”

Energy dissipation at metal surfaces

“…This simplification consequently allows for a straightforward interpolation of the friction coefficients into a convenient analytical function of the electronic density only. This distinguishes the LDFA from more refined orbital-dependent friction (ODF) methodology [114,122,127,128] whose numerical involvement [128][129][130] (until only very recently [131]) has hindered application to highdimensional models though [132][133][134][135][136][137].…”