The Dynamics of Making and Breaking Bonds at Surfaces

Luntz, A. C.

doi:10.1016/b978-044452837-7.50004-6

Cited by 19 publications

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“…ǫ F is the Fermi level, and α (or ν) indices nuclear DoF's. To date, this mean-field form of electronic friction has been applied to many systems using ab initio electronic structure theory (e.g., DFT) [17][18][19][20][21][22][23], and Langevin dynamics on a metal surface with DFT potentials has become a standard tool. We emphasize, however, that Eq.…”

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confidence: 99%

Born-Oppenheimer Dynamics, Electronic Friction, and the Inclusion of Electron-Electron Interactions

2017

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We present a universal expression for the electronic friction as felt by a set of classical nuclear degrees of freedom (DoF's) coupled to a manifold of quantum electronic DoF's; no assumptions are made regarding the nature of the electronic Hamiltonian and electron-electron repulsions are allowed. Our derivation is based on a quantum-classical Liouville equation (QCLE) for the coupled electronic-nuclear motion, followed by an adiabatic approximation whereby electronic transitions are assumed to equilibrate faster than nuclear movement. The resulting form of friction is completely general, but does reduce to previously published expressions for the quadratic Hamiltonian (i.e. Hamiltonians without electronic correlation). At equilibrium, the second fluctuation-dissipation theorem is satisfied and the frictional matrix is symmetric. To demonstrate the importance of electron-electron correlation, we study electronic friction within the Anderson-Holstein model, where a proper treatment of electron-electron interactions shows signatures of a Kondo resonance and a mean-field treatment is completely inadequate.Introduction.-The Born-Oppenheimer (BO) approximation is probably the most important framework underlying modern physics and chemistry. According to the BO approximation, for a system of nuclei and electrons, we split up the total Hamiltonian into the nuclear kinetic energy (T nuc ) and the electronic HamiltonianĤ:

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Born-Oppenheimer Dynamics, Electronic Friction, and the Inclusion of Electron-Electron Interactions

2017

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“…While these dynamics can be directly related to straightforward gas-molecule/metal scattering processes [14][15][16][17] and chemisorption/dissociation [18][19][20] , one must always remember that these dynamics can also display surprising behavior. [21][22][23][24][25][26][27] Due to electron transfer processes between molecule and metal, the charge state of the molecule need not be static and thus the Born-Oppenheimer approximation can break down 28,29 .…”

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Universality of electronic friction: Equivalence of von Oppen's nonequilibrium Green's function approach and the Head-Gordon–Tully model at equilibrium

Dou

Subotnik

2017

Phys. Rev. B

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For a molecule moving near a single metal surface at equilibrium, following von Oppen et al (Beilstein J. Nanotechnol, 3, 144 (2012)) and using a non-equilibrium Green's function (NEGF) approach, we derive a very general form of electronic friction that includes non-Condon effects. We then demonstrate that the resulting NEGF friction tensor agrees exactly with the Head-Gordon/Tully (HGT) model, provided that finite temperature effects are incorporated correctly. The present results are in agreement with our recent claim that there is only one, universal electronic friction tensor arising from the Born-Oppenheimer approximation (Phys. Rev. Lett. 119, 046001 (2017)

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“…Understanding of these fundamental surface processes and how they affect reaction rates and selectivity can in principle lead to further improvements and better design of technology. [6] Atomic and molecular beam scattering experiments combined with laser state resolved studies are powerful tools to gain deeper insights into the underlying dynamics by investigating energy transfer processes between the atomic and molecular translational and internal degrees of freedom and the phononic and electronic degrees of freedom of the surface states. [6,7] One particular area of interest is the study of the role of energy transfer from small molecules or atoms to surfaces during the adsorption process.…”

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confidence: 99%

“…[6] Atomic and molecular beam scattering experiments combined with laser state resolved studies are powerful tools to gain deeper insights into the underlying dynamics by investigating energy transfer processes between the atomic and molecular translational and internal degrees of freedom and the phononic and electronic degrees of freedom of the surface states. [6,7] One particular area of interest is the study of the role of energy transfer from small molecules or atoms to surfaces during the adsorption process. While at first the efficiency of the energy transfer (in particular the translational energy) highly affect the trapping probability of atoms or small molecules it is also of interest to understand how the transferred energy is dissipated among the energy degrees of freedom of the surface.…”

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confidence: 99%

“…As simple model systems transition metal surfaces are frequently studied, not only due to their commercial availability and thermal stability but also due to their relevance in various heterogeneous catalytic processes. [6] While such simple systems are ideal for the validation of new experimental techniques and can act as benchmark for theoretical models, another growing area in the field of surface science are the artificial design of new types of surfaces such as nanostructures.…”

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confidence: 99%

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Inelastic H-Atom scattering from ultra-thin films

Jeannette¹

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This thesis contains experimental and theoretical fundamental studies of energy transfer processes on various surfaces via inelastic hydrogen atom scattering using the Rydberg atom tagging machine. The initial investigations of in total six late transition fcc-metals (Au, Pt, Ag, Pd, Cu, Ni) allowed to establish and optimize the experimental methodology as well as to simultaneously substantiate a theoretical model for the general description of energy-transfer processes on metal surfaces. Hence, it could be determined that the energy transfer for the investigated fcc-metals predominantly takes place via electron-hole-pair excitation. Despite its smaller contribution, phonon excitation was found to be essential in order to describe the experimentally determined (H/D)-isotope effects.During the subsequently performed first hydrogen scattering experiments on insulating bulk as well as thin-layer surfaces, primarily direct inelastic scattering was observed that could be described by simple collision models. The variation of the layer thickness down to less than one monolayer of insulating aluminium oxide did not yield any significant changes of the scattering results, thus, a potential cooperative effect with the platinum substrate have been ruled out. These results as well as the scattering experiments performed on an oxygen covered Pt(111) surface would further suggest that scattering almost exclusively occurs on the quasi-isolated oxygen atoms on the surface.In a concluding series of hydrogen scattering experiments of (1 x 1) oriented graphene and partially rotated graphene on Ni(111), it was possible to study the C-H bond formation process between an impinging hydrogen atom and the graphene surfaces. The experimentally determined adsorption threshold significantly differs for both modification as well as with respect to prior studies of graphene on Pt(111), which could be explained by different interaction strengths between the graphene surface and the metal substrate.In addition, a detailed data analysis of the performed experiments further allowed to assign two new scattering components that previously had not been considered for graphene on Pt(111). i 1 Introduction Table 1.1: Selected list of Noble prize laureates in surface chemistry. [5] Nobel price laureate Year Contributions P. Sabatier 1912 "for his method of hydrogenating organic compounds in the presence of finely disintegrated metals whereby the progress of organic chemistry has been greatly advanced in recent years" F. Haber 1918 "for the synthesis of ammonia from its elements" I. Langmuir 1932 "for his discoveries and investigations in surface chemistry" C. N. Hinshelwood, 1956 "for their researches into the mechanism of N. N. Semenov chemical reactions" D. R. Herschbach, 1986 "for their contributions concerning the dynamics Y. T. Lee, J. C. Polanyi of chemical elementary processes" G. Ertl 2007 "for his studies of chemical processes on solid surfaces"Since the foundation of surface chemistry by Sabatier and Haber at the beginning of the 20 th centu...

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The Dynamics of Making and Breaking Bonds at Surfaces

Cited by 19 publications

References 401 publications

Born-Oppenheimer Dynamics, Electronic Friction, and the Inclusion of Electron-Electron Interactions

Born-Oppenheimer Dynamics, Electronic Friction, and the Inclusion of Electron-Electron Interactions

Universality of electronic friction: Equivalence of von Oppen's nonequilibrium Green's function approach and the Head-Gordon–Tully model at equilibrium

Inelastic H-Atom scattering from ultra-thin films

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