Vibrational and rotational population distribution of<mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML" display="inline"><mml:mrow><mml:msub><mml:mrow><mml:mi mathvariant="normal">D</mml:mi></mml:mrow><mml:mrow><mml:mn>2</mml:mn></mml:mrow></mml:msub></mml:mrow></mml:math>associatively desorbing from Pd(100)

Wetzig, D.; Rutkowski, M.; Zacharias, H.; Groß, Axel

doi:10.1103/physrevb.63.205412

Cited by 38 publications

(26 citation statements)

References 56 publications

(56 reference statements)

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“…A similar mechanism had previously been predicted for H 2 ϩPd(100), 8 and confirmed in recent associative desorption experiments. 9 In both the 3D and 4D calculations, we found that normal energy scaling was not obeyed, in agreement with the experimental results of Luntz et al 4 When looking at diffraction, an important difference was found between the 3D and 4D calculations. In the 3D calculations, substantial diffraction was found.…”

Section: Introductionsupporting

confidence: 80%

Reactive and diffractive scattering of H2 from Pt(111) studied using a six-dimensional wave packet method

Pijper

Kroes

Olsen

et al. 2002

The Journal of Chemical Physics

112

144

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We present results of calculations on dissociative and rotationally ͑in͒elastic diffractive scattering of H 2 from Pt͑111͒, treating all six molecular degrees of freedom quantum mechanically. The six-dimensional ͑6D͒ potential energy surface was taken from density functional theory calculations using the generalized gradient approximation and a slab representation of the metal surface. The 6D calculations show that out-of-plane diffraction is very efficient, at the cost of in-plane diffraction, as was the case in previous four-dimensional ͑4D͒ calculations. This could explain why so little in-plane diffraction was found in scattering experiments, suggesting the surface to be flat, whereas experiments on reaction suggested a corrugated surface. Results of calculations for off-normal incidence of (vϭ0,jϭ0) H 2 show that initial parallel momentum inhibits dissociation at low normal translational energies, in agreement with experiment, but has little effect for higher energies. Reaction of initial (vϭ1,jϭ0) H 2 is predicted to be vibrationally enhanced with respect to (v ϭ0,jϭ0) H 2 , as was also found in three-dimensional ͑3D͒ and 4D calculations, even though H 2 ϩPt(111) is an early barrier system.

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Section: Introductionsupporting

confidence: 80%

Reactive and diffractive scattering of H2 from Pt(111) studied using a six-dimensional wave packet method

Pijper

Kroes

Olsen

et al. 2002

The Journal of Chemical Physics

112

144

View full text Add to dashboard Cite

show abstract

“…26,35,59,66,83 In one case, the calculations 66 actually challenged the results of older experiments, 8,10 with newer experiments confirming the validity of the theoretical results. 59 Although 6D calculations have been performed for H 2 ϩPd(100) ͑Refs. 60-67͒, using a time-independent method, and for H 2 ϩCu(100) ͑Refs.…”

Section: Introductionsupporting

confidence: 48%

Signatures of site-specific reaction of H2 on Cu(100)

Somers

McCormack

Kroes

et al. 2002

The Journal of Chemical Physics

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Six-dimensional quantum dynamical calculations are presented for the reaction of (v, j) H 2 on Cu͑100͒, at normal incidence, for vϭ0 -1 and jϭ0 -5. The dynamical calculations employed a potential energy surface computed with density functional theory, using the generalized gradient approximation and a slab representation for the adsorbate-substrate system. The aim of the calculations was to establish signatures from which experiments could determine the dominant reaction site of H 2 on the surface and the dependence of the reaction site on the initial rovibrational state of H 2 . Two types of signatures were found. First, we predict that, at energies near threshold, the reaction of (vϭ1) H 2 is rotationally enhanced, because it takes place at the top site, which has an especially late barrier and a reaction path with a high curvature. On the other hand, we predict the reaction to be almost independent of j for (vϭ0) H 2 , which reacts at the bridge site. Second, we predict that, at collision energies slightly above threshold for which the reaction probabilities of the (vϭ0) and (vϭ1) states are comparable, the rotational quadrupole alignment of (vϭ1) reacting molecules should be larger than that of (vϭ0) reacting molecules, for jϭ1, 4, and 5. For ( j ϭ2) H 2 , the opposite should be true, and for ( jϭ3) H 2 , the rotational quadrupole alignment should be approximately equal for (vϭ1) and (vϭ0) H 2 . These differences can all be explained by the difference in the predicted reaction site for (vϭ1) and (vϭ0) H 2 ͑top and bridge͒ and by the differences in the anisotropy of the potential at the reaction barrier geometries associated with these sites. Our predictions can be tested in associative desorption experiments, using currently available experimental techniques.

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“…Earlier experiments 19 had yielded very large values that were later questioned by the quantum calculations. 51 More refined experiments 23 have now confirmed the theoretical results, showing that theory is now able to make quantitative predictions for reaction that may even lead to a reconsideration of experiments. Figure 4D also shows good agreement between theory and experiment for rotational temperatures.…”

mentioning

confidence: 51%

Quantum Theory of Dissociative Chemisorption on Metal Surfaces

et al. 2002

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Recent theoretical progress in gas-surface reaction dynamics, a field relevant to heterogeneous catalysis, is described. One of the most fundamental reactions, the dissociative chemisorption of H2 on metal surfaces, can now be treated accurately using quantum mechanics. Density functional theory is used to compute the molecule-surface interaction, and the motion of the hydrogen atoms is simulated using quantum dynamics, modeling all six molecular degrees of freedom. Theory is in good quantitative agreement with molecular beam experiments, offering useful interpretations, and allowing reliable predictions. The success of the approach calls for extensions to larger systems, such as dissociative chemisorption of polyatomic molecules.

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Vibrational and rotational population distribution ofD2associatively desorbing from Pd(100)

Cited by 38 publications

References 56 publications

Reactive and diffractive scattering of H2 from Pt(111) studied using a six-dimensional wave packet method

Reactive and diffractive scattering of H2 from Pt(111) studied using a six-dimensional wave packet method

Signatures of site-specific reaction of H2 on Cu(100)

Quantum Theory of Dissociative Chemisorption on Metal Surfaces

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