Role of Vibrationally Excited NO in Promoting Electron Emission When Colliding with a Metal Surface:  A Nonadiabatic Dynamic Model

Katz, Gil; Zeiri, Yehuda; Kosloff, Ronnie

doi:10.1021/jp052107k

Cited by 18 publications

(20 citation statements)

References 33 publications

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“…The dashed-line fit to the data of Fig. 2 for NO(V = 0) shows that our results for the ground vibrational state conform to the velocity dependence previously reported for other systems and so provides a validation of our experimental method (24)(25)(26).…”

supporting

confidence: 86%

“…Katz et al have treated the problem of vibrationally promoted electron emission (26) by NO on Cs/Ru. Though some aspects of the experimental observations are captured in that workfor example, the positive dependence on initial vibrational excitation-like other theories of nonadiabatic interactions at surfaces, their theory predicts an increase of electron emission with increasing velocity.…”

mentioning

confidence: 99%

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Inverse Velocity Dependence of Vibrationally Promoted Electron Emission from a Metal Surface

Nahler

White

LaRue

et al. 2008

Science

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All previous experimental and theoretical studies of molecular interactions at metal surfaces show that electronically nonadiabatic influences increase with molecular velocity. We report the observation of a nonadiabatic electronic effect that follows the opposite trend: The probability of electron emission from a low-work function surface--Au(111) capped by half a monolayer of Cs--increases as the velocity of the incident NO molecule decreases during collisions with highly vibrationally excited NO(X(2)pi((1/2)), V = 18; V is the vibrational quantum number of NO), reaching 0.1 at the lowest velocity studied. We show that these results are consistent with a vibrational autodetachment mechanism, whereby electron emission is possible only beyond a certain critical distance from the surface. This outcome implies that important energy-dissipation pathways involving nonadiabatic electronic excitations and, furthermore, not captured by present theoretical methods may influence reaction rates at surfaces.

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supporting

confidence: 86%

mentioning

confidence: 99%

Inverse Velocity Dependence of Vibrationally Promoted Electron Emission from a Metal Surface

Nahler

White

LaRue

et al. 2008

Science

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“…In principle, dissipative effective two-state models ͑which implicitly account for continua͒ or nondissipative multistate models ͑which explicitly account for continua͒ could be used for this purpose. This has been done, for example, for scattering of NO from metals, 24,25 and for hotelectron mediated photodesorption of NO from Pt͑111͒ ͑Refs. 26-28͒ in the past.…”

Section: ͑3͒mentioning

confidence: 99%

Role of electronic friction during the scattering of vibrationally excited nitric oxide molecules from Au(111)

Monturet

Saalfrank

2010

Phys. Rev. B

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Some time ago, it has been observed that vibrationally highly excited NO͑v͒ molecules ͑with typical vibrational quantum numbers v Ϸ 15͒ lose substantial amounts of vibrational energy when scattering off a Au͑111͒ surface ͓H. Huang, C. Rettner, D. Auerbach, and A. Wodtke, Science 290, 111 ͑2000͔͒. This has been interpreted as a sign for the breakdown of the Born-Oppenheimer approximation due to vibration-electron coupling. It has been argued that this process cannot be understood on the basis of single-quantum transitions which are typical for "electronic friction" models based on a perturbative treatment of weak vibration-electron couplings. Rather, multiple-quanta transitions characteristic for strong nonadiabatic effects are needed according to recent classical surface hopping calculations involving multiple potential-energy surfaces and model Hamiltonians ͓N. Shenvi, S. Roy, and J. C. Tully, Science 326, 829 ͑2009͔͒. Here we address the importance and magnitude of electronic friction for NO@ Au͑111͒ by using fully quantum-mechanical, parameter-free first-principles theories in reduced dimensions. Periodic density-functional theory calculations are performed to obtain a ground-state potential-energy surface along the desorption and NO-vibration coordinates, and coordinate-resolved, finite NO vibrational lifetimes due to vibration-electron coupling. Using this input, the scattering event is modeled by open-system density-matrix theory in the frame of the coupled-channel-densitymatrix method, which allows for the inclusion of energy relaxation of the scattering NO molecules. It is found that within this model at least, electronic friction accounts for the observed vibrational deactivation of NO scattering from gold.

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“…7 Nonadiabatic dynamics was employed by Katz et al to simulate the vibrational relaxation of NO scattering from Cs/Ru using three coupled potential energy diabats representing the NO, NO − , and NO+ e − electronic states. 8 Li et al 9 have used a two-state model based on work by Gadzuk 10 to calculate vibrational relaxation of NO scattering from Au, using a method of quantum jumps between NO and NO − diabatic states. In Ref.…”

Section: Introductionmentioning

confidence: 99%

“…The importance of a transient negative ion has been suggested previously. 8,11 The second critical feature is inclusion of a strong electronic energy dependence of the overlap of metal electronic wave functions with the molecule. Electronic wave functions penetrate farther into the vacuum region above the surface as their energy increases above the Fermi level.…”

Section: Introductionmentioning

confidence: 99%

Vibrational relaxation of NO on Au(111) via electron-hole pair generation

Shenvi

Roy

Parandekar

et al. 2006

The Journal of Chemical Physics

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Recent experiments have demonstrated the breakdown of the Born-Oppenheimer approximation when NO undergoes inelastic scattering from a Au(111) surface. In this paper, we provide a simple theoretical model for understanding this phenomenon. Our model predicts multiquanta vibrational relaxation through the creation of high-energy electron-hole pair excitations in the metal. Using experimentally determined parameters, our model gives qualitatively accurate predictions for the final vibrational state populations of the scattered molecule and predicts efficient conversion of vibrational energy into electronic energy.

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Role of Vibrationally Excited NO in Promoting Electron Emission When Colliding with a Metal Surface: A Nonadiabatic Dynamic Model

Cited by 18 publications

References 33 publications

Inverse Velocity Dependence of Vibrationally Promoted Electron Emission from a Metal Surface

Inverse Velocity Dependence of Vibrationally Promoted Electron Emission from a Metal Surface

Role of electronic friction during the scattering of vibrationally excited nitric oxide molecules from Au(111)

Vibrational relaxation of NO on Au(111) via electron-hole pair generation

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