Vibrational Promotion of Electron Transfer

Huang, Yuhui; Rettner, Charles; Auerbach, Daniel J.; Wodtke, Alec M.

doi:10.1126/science.290.5489.111

Cited by 312 publications

(383 citation statements)

References 33 publications

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“…Experimental results showed that NO in high vibrational states (v i = 15), incident with translational energy of 0.05 eV, relax into a broad range of vibrational states when scattered from a gold surface. 16 Several different theoretical approaches semi-quantitatively reproduce the observed vibrational state distributions, including a Monte Carlo model with stochastic quantum jumps between the neutral and negative ion states of the molecule, 17 fully quantum mechanical first-principles EF theory, 18 and molecular dynamics (MD) employing Independent Electron Surface Hopping (IESH) on a density functional theory (DFT) based Newns-Anderson Hamiltonian. [19][20][21][22] In order to attempt to distinguish between these various theoretical approaches, a comprehensive series of experiments was performed to study the collision-induced vibrational excitation of NO(v = 0) into vibrational states v = 1, 2 when scattered from a Au(111) surface over a wide range of incidence energies and surface temperatures (300 K ≤ T s ≤ 1000 K and 0.11 eV ≤ E i ≤ 1.05 eV).…”

Section: Introductionmentioning

confidence: 99%

The importance of accurate adiabatic interaction potentials for the correct description of electronically nonadiabatic vibrational energy transfer: A combined experimental and theoretical study of NO(v = 3) collisions with a Au(111) surface

Golibrzuch

Shirhatti

Rahinov

et al. 2014

The Journal of Chemical Physics

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We present a combined experimental and theoretical study of NO(v = 3 → 3, 2, 1) scattering from a Au(111) surface at incidence translational energies ranging from 0.1 to 1.2 eV. Experimentally, molecular beam-surface scattering is combined with vibrational overtone pumping and quantumstate selective detection of the recoiling molecules. Theoretically, we employ a recently developed first-principles approach, which employs an Independent Electron Surface Hopping (IESH) algorithm to model the nonadiabatic dynamics on a Newns-Anderson Hamiltonian derived from density functional theory. This approach has been successful when compared to previously reported NO/Au scattering data. The experiments presented here show that vibrational relaxation probabilities increase with incidence energy of translation. The theoretical simulations incorrectly predict high relaxation probabilities at low incidence translational energy. We show that this behavior originates from trajectories exhibiting multiple bounces at the surface, associated with deeper penetration and favored (N-down) molecular orientation, resulting in a higher average number of electronic hops and thus stronger vibrational relaxation. The experimentally observed narrow angular distributions suggest that mainly single-bounce collisions are important. Restricting the simulations by selecting only single-bounce trajectories improves agreement with experiment. The multiple bounce artifacts discovered in this work are also present in simulations employing electronic friction and even for electronically adiabatic simulations, meaning they are not a direct result of the IESH algorithm. This work demonstrates how even subtle errors in the adiabatic interaction potential, especially those that influence the interaction time of the molecule with the surface, can lead to an incorrect description of electronically nonadiabatic vibrational energy transfer in molecule-surface collisions. © 2014 AIP Publishing LLC. [http://dx

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Section: Introductionmentioning

confidence: 99%

The importance of accurate adiabatic interaction potentials for the correct description of electronically nonadiabatic vibrational energy transfer: A combined experimental and theoretical study of NO(v = 3) collisions with a Au(111) surface

Golibrzuch

Shirhatti

Rahinov

et al. 2014

The Journal of Chemical Physics

Self Cite

111

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“…Experiments developed during the last few years have measured, for example, chemicurrents and creation of hot electrons during the chemisorption of atoms and molecules on metal films and surfaces, [1][2][3][4][5] highly efficient multi-quantum vibrational relaxation of highly vibrationally excited NO molecules scattered from metal surfaces, 6,7 and even electron emission upon scattering of highly vibrationally excited NO from a low work function metal surface. 8 Nevertheless, the fundamental question to be answered now is: how much does the presence of electronic excitations influence the interactions between molecules and metal surfaces?…”

Section: Introductionmentioning

confidence: 99%

Vibrational deexcitation and rotational excitation of H2 and D2 scattered from Cu(111): Adiabatic versus non-adiabatic dynamics

Muzas

Juaristi

Alducin

et al. 2012

The Journal of Chemical Physics

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We have studied survival and rotational excitation probabilities of H 2 (v i = 1, J i = 1) and D 2 (v i = 1, J i = 2) upon scattering from Cu(111) using six-dimensional (6D) adiabatic (quantum and quasi-classical) and non-adiabatic (quasi-classical) dynamics. Non-adiabatic dynamics, based on a friction model, has been used to analyze the role of electron-hole pair excitations. Comparison between adiabatic and non-adiabatic calculations reveals a smaller influence of non-adiabatic effects on the energy dependence of the vibrational deexcitation mechanism than previously suggested by low-dimensional dynamics calculations. Specifically, we show that 6D adiabatic dynamics can account for the increase of vibrational deexcitation as a function of the incidence energy, as well as for the isotope effect observed experimentally in the energy dependence for H 2 (D 2 )/Cu(100). Furthermore, a detailed analysis, based on classical trajectories, reveals that in trajectories leading to vibrational deexcitation, the minimum classical turning point is close to the top site, reflecting the multidimensionally of this mechanism. On this site, the reaction path curvature favors vibrational inelastic scattering. Finally, we show that the probability for a molecule to get close to the top site is higher for H 2 than for D 2 , which explains the isotope effect found experimentally.

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“…Since the shape of the molecule changes upon charge transfer, state to state electron transfer rates are often controlled by intramolecular vibrational motion [13][14][15]. While in many cases the outcome of a reaction at high collision energies is well described by the properties of the isolated molecule the results at low energies are not explained by a Frank-Condon treatment [16,17].…”

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confidence: 99%

Differential Scattering Cross-Sections for the Different Product Vibrational States in the Ion-Molecule ReactionAr++N2

et al. 2013

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The charge transfer reaction Ar + + N2 → Ar + N + 2 has been investigated in a crossed beam experiment in combination with three-dimensional velocity map imaging. Angular differential stateto-state cross sections were determined as a function of the collision energy. We found that scattering into the first excited vibrational level dominates as expected, but only for scattering in the forward direction. Higher vibrational excitations up to v ′ = 6 have been observed for larger scattering angles. For decreasing collision energy, scattering into higher scattering angles becomes increasingly important for all kinematically allowed quantum states. Our detailed measurements indicate that a quantitative agreement between experiment and theory for this basic ion-molecule reaction now comes within reach.Gas phase studies of ion-molecule reactions have provided insight into a multitude of chemical processes in environments where ions and neutrals coexist. Ion-molecule reactions determine the abundance of many of the complex species that can be detected in interstellar molecular clouds and in planetary atmospheres [1,2]. The conceptually simple charge transfer reactions are particularly interesting, as they were found to explain the X-ray emission from comets [3,4] and may serve as a possible acceleration mechanism of cosmic rays due to strong shock waves in supernova remnants [5]. Charge transfer is also of cosmological importance in that it shapes the hydrogen chemistry in the early universe [6]. Laboratory measurements and theoretical calculations are needed to provide the basis for modeling these processes. In addition charge transfer reactions lead to characteristic light emission from excited states that are useful to determine the parameters of laboratory or technical plasmas, such as temperature, velocity, electron density and charge states of ions [7,8]. To reach very low collision energies, charge transfer has been studied near threshold in half collisions [9]. Recently, ultracold charge transfer reactions have become of interest in studies of cold atom-ion collisions, which are carried out to investigate quantum mechanical phenomena in scattering processes at very low energies [10][11][12].Charge transfer reactions in gas phase evolve in many cases not on a single potential energy surface and are therefore often accompanied by a breakdown of the BornOppenheimer approximation. Since the shape of the molecule changes upon charge transfer, state to state electron transfer rates are often controlled by intramolecular vibrational motion [13][14][15]. While in many cases the outcome of a reaction at high collision energies is well described by the properties of the isolated molecule the results at low energies are not explained by a Frank-Condon treatment [16,17]. This behavior may be explained by molecular bond distortions due to the electric field of the incoming ion [18] and to short range repulsive interactions between the projectile and the target [19].A model system of a gas phase non-Born-Oppenheimer reaction ...

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Vibrational Promotion of Electron Transfer

Cited by 312 publications

References 33 publications

The importance of accurate adiabatic interaction potentials for the correct description of electronically nonadiabatic vibrational energy transfer: A combined experimental and theoretical study of NO(v = 3) collisions with a Au(111) surface

The importance of accurate adiabatic interaction potentials for the correct description of electronically nonadiabatic vibrational energy transfer: A combined experimental and theoretical study of NO(v = 3) collisions with a Au(111) surface

Vibrational deexcitation and rotational excitation of H2 and D2 scattered from Cu(111): Adiabatic versus non-adiabatic dynamics

Differential Scattering Cross-Sections for the Different Product Vibrational States in the Ion-Molecule ReactionAr++N2

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