Vibrational Inelasticity of Highly Vibrationally Excited NO on Ag(111)

Abstract

Multiquantum relaxation of highly vibrationally excited nitric oxide on noble metals has become one of the best studied examples of the Born-Oppenheimer approximation's failure to describe molecular interactions at metal surfaces. When first reported, relaxation of highly vibrationally excited NO occurring in collisions with Au(111) surfaces exhibited the largest vibrational inelasticity seen in molecule-surface collisions, and no system has been found to date exhibiting a greater vibrational inelasticity. In this work, we compare the relaxation of NO(v = 11) in scattering events on Ag(111) to that on Au(111). The relaxation probability and the average vibrational energy loss are much higher when scattering from Ag(111). We discuss possible reasons for this remarkable phenomenon, which may be related to the dissociation of NO, possible on Ag(111) at lower energy compared with Au(111).

Electron transfer mediates vibrational relaxation of CO in collisions with Ag(111)

“…8 Panel (a): Relaxation probability of various molecule-surface systems as a function of E v (r out ) À F at an incidence translational energy of 0.6 eV. In addition to CO(v i = 17)/Ag(111), results are shown for CO(v i = 17)/ Au(111), 33 CO(v i = 2)/Ag(111), 32 CO(v i = 2)/Au(111), 11 NO(v i = 11)/Ag(111), 31 NO(v i = 3, 11, 16)/Au(111), 12 and NO(v i = 2) on thin films of Ag on Au(111). 32 All systems follow a common trend showing an increase of the relaxation probability from 0 to 1 between À5.25 eV and À3.5 eV.…”

“…For NO(v), vibrational inelasticity has been studied on Au(111) and Ag(111)-the vibrational relaxation probability of highly vibrationally excited NO is significantly higher at Ag(111) (F = 4.7 eV) than at Au(111) (F = 5.3 eV). 31 Furthermore, varying the thickness of atomically defined Ag thin films on Au(111) showed a clear correlation between vibrational relaxation probability and surface work function. 32 We have also employed P 3 D to study scattering of CO(v = 17) from Au(111).…”

Computational approaches to dissociative chemisorption on metals: towards chemical accuracy

“…229 Vibrationally inelastic scattering of NO from metal surfaces has become a benchmark system for electronically non-adiabatic scattering from metal surfaces, 230,231 which continues to receive attention. [232][233][234] A host of experiments also exists on the reactive and inelastic scattering of polyatomic molecules from metal surfaces. The DC of methane and its isotopologues has become a paradigm for non-statistical reactive scattering.…”

Surface-Sensitive and Surface-Specific Ultrafast Two-Dimensional Vibrational Spectroscopy

“…We have examined this effect 177 Significant interest exists in the characterization of highly excited vibrational states from different experimental and theoretical perspectives, since this represents a concentration of a large amounts of vibrational energy in a single chemical bond. 55,89,90,305,[374][375][376][377][378][379][380][381] A particular focus lies on the mechanism of preparation of these states and how highly excited molecules dissipate the excess energy to the environment. The energy can for instance be transferred to the substrate and its phonon bath, leading to an increase in the sample temperature.…”