On the Structure Sensitivity of Direct NO Decomposition over Low-Index Transition Metal Facets

Falsig, Hanne; Shen, Juan; Khan, Tuhin Suvra; Guo, Wei; Jones, Glenn; Dahl, Søren; Bligaard, Thomas

doi:10.1007/s11244-013-0164-5

Cited by 78 publications

(113 citation statements)

References 37 publications

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“…25,28 We note that the dissociation barrier of NO on Au(111) has been calculated by DFT methods to be higher than 3 eV. 24 Specifically, in Fig. 6 we compare the surface-temperature dependence of the NO(v = 0 → 1) 28,32 and NO(v = 2 → 3) 35 channels at E i = 0.41 eV to the HCl(v = 0 → 1) and HCl(v = 1 → 2) at 0.67 eV.…”

Section: Results and Analysismentioning

confidence: 91%

“…The NO/Au(111) system is well known for its strong electronically nonadiabatic vibrational energy transfer. However, the dissociation barrier (∼3 eV 24 ) is energetically not accessible under the conditions employed. Our results suggest that for HCl/Au(111) both V-T and V-EHP coupling are dramatically enhanced in the vicinity of the transition state for dissociative adsorption at a metal surface, even when the collision trajectory fails to pass over it.…”

Section: Introductionmentioning

confidence: 99%

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Vibrational energy transfer near a dissociative adsorption transition state: State-to-state study of HCl collisions at Au(111)

Geweke

Shirhatti

Rahinov

et al. 2016

The Journal of Chemical Physics

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Articles you may be interested inThe 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) In this work we seek to examine the nature of collisional energy transfer between HCl and Au(111) for nonreactive scattering events that sample geometries near the transition state for dissociative adsorption by varying both the vibrational and translational energy of the incident HCl molecules in the range near the dissociation barrier. Specifically, we report absolute vibrational excitation probabilities for HCl(v = 0 → 1) and HCl(v = 1 → 2) scattering from clean Au(111) as a function of surface temperature and incidence translational energy. The HCl(v = 2 → 3) channel could not be observed-presumably due to the onset of dissociation. The excitation probabilities can be decomposed into adiabatic and nonadiabatic contributions. We find that both contributions strongly increase with incidence vibrational state by a factor of 24 and 9, respectively. This suggests that V-T as well as V-EHP coupling can be enhanced near the transition state for dissociative adsorption at a metal surface. We also show that previously reported HCl(v = 0 → 1) excitation probabilities [Q. Ran et al., Phys. Rev. Lett. 98, 237601 (2007)]-50 times smaller than those reported here-were influenced by erroneous assignment of spectroscopic lines used in the data analysis. Published by AIP Publishing. [http://dx

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Section: Results and Analysismentioning

confidence: 91%

Section: Introductionmentioning

confidence: 99%

Vibrational energy transfer near a dissociative adsorption transition state: State-to-state study of HCl collisions at Au(111)

Geweke

Shirhatti

Rahinov

et al. 2016

The Journal of Chemical Physics

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“…Here,the b value for NÀNbond breaking is 0.56 eV lower on the step,whereas the b values for the hydrogenation steps are between 0.29 eV and 0.42 eV lower on the terrace. [15,20] Figure 3s hows the TOFm aps and the bifunctional gain resulting from adetailed microkinetic model employing these parameters and considering diffusional coupling between the two facets (see also Section S3). Thea bsolute bifunctional gain found for this system is only about af actor of 1.1 and therefore much lower than the gain found for the model reaction.…”

Section: Angewandte Chemiementioning

confidence: 99%

“…Figure 2s hows the TOF maps and the relative bifunctional gains when specifically using the BEP parameters representative for NO decomposition on ametal(111) facet. [20] Even though huge relative bifunctional gains can again be found towards the extreme regions of descriptor values,t hey nevertheless still correspond to an insignificant absolute catalytic activity (compare the left and middle panels). We note that our findings are expected to hold also for high coverages where lateral interactions become significant, as such interactions typically do not change the BEP relations,b ut merely lead to as hift in the adsorption energies.…”

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confidence: 96%

Analyzing the Case for Bifunctional Catalysis

et al. 2016

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Bifunctional coupling of two different catalytic site types has often been invoked to explain experimentally observed enhanced catalytic activities. We scrutinize such claims with generic scaling-relation-based microkinetic models that allow exploration of the theoretical limits for such a bifunctional gain for several model reactions. For sites at transition-metal surfaces, the universality of the scaling relations between adsorption energies largely prevents any improvements through bifunctionality. Only the consideration of systems that involve the combination of different materials, such as metal particles on oxide supports, offers hope for significant bifunctional gains.

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“…21 for NO(v = 15) relaxation does not accurately describe NO dissociation, comparison to experiment can be misleading. This is a particular concern in light of recent calculations that place the activation energy for NO dissociation on Au(111) near 3.5 eV, 28 which is close to the vibrational energy of NO(v = 15). As DFT is known to sometimes have problems in the accurate determination of activation energies, one should consider a test of electronically nonadiabatic theories that is expected to be less sensitive to such errors in the adiabatic interaction potential.…”

Section: Introductionmentioning

confidence: 96%

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

111

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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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On the Structure Sensitivity of Direct NO Decomposition over Low-Index Transition Metal Facets

Cited by 78 publications

References 37 publications

Vibrational energy transfer near a dissociative adsorption transition state: State-to-state study of HCl collisions at Au(111)

Vibrational energy transfer near a dissociative adsorption transition state: State-to-state study of HCl collisions at Au(111)

Analyzing the Case for Bifunctional Catalysis

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

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