Chemically Accurate Simulation of a Polyatomic Molecule-Metal Surface Reaction

Nattino, Francesco; Migliorini, Davide; Kroes, Geert–Jan; Dombrowski, Eric; High, Eric A.; Killelea, Daniel R.; Utz, A. L.

doi:10.1021/acs.jpclett.6b01022

Cited by 107 publications

(303 citation statements)

References 43 publications

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“…Important steps towards an accurate, yet efficient firstprinciples-based modeling of the energy uptake into phononic d.o.f. have recently been taken [3][4][5][6][7][8][9][10]. In contrast, the explicit description of e-h pair excitations and corresponding nonadiabatic couplings directly from first principles still poses a formidable challenge.…”

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confidence: 99%

Nonadiabatic Vibrational Damping of Molecular Adsorbates: Insights into Electronic Friction and the Role of Electronic Coherence

2017

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We present a perturbation approach rooted in time-dependent density-functional theory to calculate electron-hole (e-h) pair excitation spectra during the nonadiabatic vibrational damping of adsorbates on metal surfaces. Our analysis for the benchmark systems CO on Cu(100) and Pt(111) elucidates the surprisingly strong influence of rather short electronic coherence times. We demonstrate how in the limit of short electronic coherence times, as implicitly assumed in prevalent quantum nuclear theories for the vibrational lifetimes as well as electronic friction, band structure effects are washed out. Our results suggest that more accurate lifetime or chemicurrentlike experimental measurements could characterize the electronic coherence. DOI: 10.1103/PhysRevLett.119.176808 The tortuous ways in which kinetic and chemical energy is transferred between adsorbates and substrate atoms fundamentally govern the dynamics of surface chemical reactions, for instance, in the context of heterogeneous catalysis or advanced deposition techniques. For metal substrates, the two main energy dissipation mechanisms in this regard are the adsorbate interaction with lattice vibrations, i.e., substrate phonons, and the excitation of electronhole (e-h) pairs. The latter are attributable to the nonadiabatic coupling of nuclear motion to the substrate electronic degrees of freedom (d.o.f.) and seem to be substantial in order to rationalize an increasing number of experimental findings [1,2]. Important steps towards an accurate, yet efficient firstprinciples-based modeling of the energy uptake into phononic d.o.f. have recently been taken [3][4][5][6][7][8][9][10]. In contrast, the explicit description of e-h pair excitations and corresponding nonadiabatic couplings directly from first principles still poses a formidable challenge.In this regard, electronic friction theory (EFT) [11,12] has become a popular workhorse to effectively capture the effects of such nonadiabatic energy loss on the adsorbate dynamics in a computationally convenient way [13][14][15][16][17][18][19]. Inspired by vibrational lifetimes obtained via response theory [20] or Fermi's golden rule in the nuclear system [21], a Langevin equation for the nuclei emerges from a semiclassical picture implying complete electronic decoherence in terms of the Markov approximation [12]. This approach thus avoids an explicit propagation of the electron dynamics and concomitant ultrafast time scales by coarse-graining the effects into electronic friction forces linear in nuclear velocities. This enables an efficient combination even with density-functional theory (DFT) based ab initio molecular dynamics (AIMD) simulations on high-dimensional potential energy surfaces as required for surface dynamical studies [15,22,23].Independent of the particular recipe employed to obtain the electronic friction coefficients [12,14,17,20,24,25], however, the downside of the coarse-graining of the electron dynamics is that it precludes a more fundamental understanding of the underlying e-h pair excit...

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confidence: 99%

Nonadiabatic Vibrational Damping of Molecular Adsorbates: Insights into Electronic Friction and the Role of Electronic Coherence

2017

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“…Rather than using a quantum approach to propagate the dynamics, Kroes and coworkers (22,(139)(140)(141)(142)(143)(144) use quasi-classical trajectory calculations in their ab initio molecular dynamics (AIMD) simulations of gas-surface reactions. One advantage of the AIMD treatment is that it includes all molecular degrees of freedom as well as the surface-atom motion, which is not yet possible using quantum dynamics.…”

Section: Discussionmentioning

confidence: 99%

Quantum State–Resolved Studies of Chemisorption Reactions

Chadwick

Beck

2017

Annu. Rev. Phys. Chem.

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Chemical reactions at the gas-surface interface are ubiquitous in the chemical industry as well as in nature. Investigating these processes at a microscopic, quantum state-resolved level helps develop a predictive understanding of this important class of reactions. In this review, we present an overview of the field of quantum state-resolved gas-surface reactivity measurements that explore the role of the initial quantum state on the dissociative chemisorption of a gas-phase reactant incident on a solid surface. Using molecular beams and either quantum state-specific reactant preparation or product detection by laser excitation, these studies have observed mode specificity and bond selectivity as well as steric effects in chemisorption reactions, highlighting the nonstatistical and complex nature of gas-surface reaction dynamics.

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“…8,11,12,21 However, if E trans is high, close to the minimum barrier for dissociation, setting S v=0 0 = S laser-off 0 may be a better approximation and this was applied when calculating S ν 3 0 using Equation (3). 16,24 The value of S ν 3 0 obtained using this approximation will be an upper limit.…”

Section: State Resolved King and Wells Measurementsmentioning

confidence: 92%

“…Utz et al have used K&W to investigate the dissociative chemisorption of methane on Ni(111) with quantum state resolution. 16 Here we report the first application of the K&W technique to the dissociative chemisorption of CH 4 on Pt(111), a system where vibrational excitation enhances the reactivity less strongly than for CH 4 on Ni(111). 15,47 The remainder of the paper is organized as follows.…”

Section: Introductionmentioning

confidence: 99%

“…First principles theory combined with classical and quantum dynamics simulations is able to reproduce at least qualitatively many of the experimental observations. [15][16][17][18][19][20][21][22] Several techniques have been developed to measure sticking coefficients with quantum state resolution, for example, by detecting the surface bound products using Auger electron spectroscopy, 5,6,23,24 reflection absorption infrared spectroscopy, 7,11,15,21 or titration of the adsorbates to make molecules that desorb and can be detected in the gas phase mass spectrometrically. 9,12,22,25 Whilst these have proved to be powerful techniques for determining quantum state resolved sticking coefficients, they share a common disadvantage in that calibrations are necessary to quantify the adsorbate coverage and number of molecules incident on the surface, both of which need to be known to accurately determine the sticking coefficient.…”

Section: Introductionmentioning

confidence: 99%

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Quantum state resolved molecular beam reflectivity measurements: CH4 dissociation on Pt(111)

Chadwick

Gutiérrez-González

Beck

2016

The Journal of Chemical Physics

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The King and Wells molecular beam reflectivity method has been used for a quantum state resolved study of the dissociative chemisorption of CH4 on Pt(111) at several surface temperatures. Initial sticking coefficients S0 were measured for incident CH4 prepared both with a single quantum of ν3 antisymmetric stretch vibration by infrared laser pumping and without laser excitation. Vibrational excitation of the ν3 mode is observed to be less efficient than incident translational energy in promoting the dissociation reaction with a vibrational efficacy ην3 = 0.65. The initial state resolved sticking coefficient S0ν3 was found to be independent of the surface temperature over the 50 kJ/mol to 120 kJ/mol translational energy range studied here. However, the surface temperature dependence of the King and Wells data reveals the migration of adsorbed carbon formed by CH4 dissociation on the Pt(111) surface leading to the growth of carbon particles.

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Chemically Accurate Simulation of a Polyatomic Molecule-Metal Surface Reaction

Cited by 107 publications

References 43 publications

Nonadiabatic Vibrational Damping of Molecular Adsorbates: Insights into Electronic Friction and the Role of Electronic Coherence

Nonadiabatic Vibrational Damping of Molecular Adsorbates: Insights into Electronic Friction and the Role of Electronic Coherence

Quantum State–Resolved Studies of Chemisorption Reactions

Quantum state resolved molecular beam reflectivity measurements: CH4 dissociation on Pt(111)

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