Vibrational excitation of NO scattered from Cu(110)

Watts, Eleanor; Siders, Jennifer L. W.; Sitz, Greg O.

doi:10.1016/s0039-6028(96)01194-6

Cited by 43 publications

(58 citation statements)

References 21 publications

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“…6 and 7 illustrate the approach to thermal equilibrium where the exact solutions, eqn (12), are plotted as a function of the interaction time and surface temperature, respectively, approaching the maximum possible value of 1 2 given by (13d). It is thus clear that the Arrhenius surface temperature dependence of the single-quantum vibrational excitation probability observed experimentally 1,[17][18][19] can be reproduced by a kinetic model (9)-(10) with the analytical expression (5) for the rate of electronically mediated vibrational energy transfer introduced in this work.…”

Section: Kinetics and Absolute Excitation Probabilitiesmentioning

confidence: 76%

“…a 01 = a 10 = a 12 = a 21 = 1, a 02 = a 20 = b Â a 01 (19) and the factor b accounts for the relative importance of direct single-step NO(v = 0 -1) and overtone NO(v = 0 -2) excitation. With such a choice of numerical values for the coefficients a vv 0 the solutions of (17) will be expressed in units of time t given by t = a 01 t…”

Section: Full Model and Fit To Experimental Datamentioning

confidence: 99%

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On the temperature dependence of electronically non-adiabatic vibrational energy transfer in molecule–surface collisions

Matsiev

Cooper

et al. 2011

Phys. Chem. Chem. Phys.

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Here we extend a recently introduced state-to-state kinetic model describing single-and multi-quantum vibrational excitation of molecular beams of NO scattering from a Au(111) metal surface. We derive an analytical expression for the rate of electronically non-adiabatic vibrational energy transfer, which is then employed in the analysis of the temperature dependence of the kinetics of direct overtone and two-step sequential energy transfer mechanisms. We show that the Arrhenius surface temperature dependence for vibrational excitation probability reported in many previous studies emerges as a low temperature limit of a more general solution that describes the approach to thermal equilibrium in the limit of infinite interaction time and that the pre-exponential term of the Arrhenius expression can be used not only to distinguish between the direct overtone and sequential mechanisms, but also to deduce their relative contributions. We also apply the analytical expression for the vibrational energy transfer rates introduced in this work to the full kinetic model and obtain an excellent fit to experimental data, the results of which show how to extract numerical values of the molecule-surface coupling strength and its fundamental properties.

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Section: Kinetics and Absolute Excitation Probabilitiesmentioning

confidence: 76%

Section: Full Model and Fit To Experimental Datamentioning

confidence: 99%

On the temperature dependence of electronically non-adiabatic vibrational energy transfer in molecule–surface collisions

Matsiev

Cooper

et al. 2011

Phys. Chem. Chem. Phys.

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“…Interested readers are referred to a recent review (6). It includes experimental signatures in the surface temperature and incidence translational energy dependence of the probability of vibrationally state changing collisions (14,15,17,34,35). Multiquantum vibrational relaxation has been directly attributed to vibrational promotion of ET (14).…”

Section: Discussionmentioning

confidence: 99%

Observation of orientation-dependent electron transfer in molecule–surface collisions

Bartels

Golibrzuch

Bartels

et al. 2013

Proc. Natl. Acad. Sci. U.S.A.

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Molecules typically must point in specific relative directions to participate efficiently in energy transfer and reactions. For example, Förster energy transfer favors specific relative directions of each molecule's transition dipole [Förster T (1948) Ann Phys 2(1-2):55-75] and electron transfer between gas-phase molecules often depends on the relative orientation of orbitals [Brooks PR, et al. (2007) J Am Chem Soc 129(50):15572-15580]. Surface chemical reactions can be many orders of magnitude faster than their gas-phase analogs, a fact that underscores the importance of surfaces for catalysis. One reason surface reactions can be so fast is the labile change of oxidation state that commonly takes place upon adsorption, a process involving electron transfer between a solid metal and an approaching molecule. By transferring electrons to or from the adsorbate, the process of bond weakening and/or cleavage is initiated, chemically activating the reactant [Yoon B, et al. (2005) (111) surface with the N atom oriented toward the surface. This represents a rare opportunity to investigate the steric influences on an electron transfer reaction happening at a surface.dynamics at surfaces | orientation of molecules | rotational rainbow T he measurement of the orientation dependence of reaction rates can provide a sensitive test of theories of chemical processes. Electron transfer (ET) reactions are of particular interest in this regard, both because of the fundamental issues they pose involving subtle long-range orientation-dependent interactions, and because of the importance of ET in a remarkably wide range of phenomena. Long-range ET reactions play an important role in living systems (1). They are important in catalysis on metals and zeolites (2), in rechargeable batteries, in corrosion (3), and in photosynthesis (4).On metal surfaces, an ET reaction may proceed by transient formation of a molecular anion via excitation of electronic states of the metal, often precluding a description of the reaction mechanism within an adiabatic picture based on the BornOppenheimer approximation (5, 6). As in the analogy to whaling used in naming gas-phase ET reactions, this process of an electron jump from the surface to an approaching molecule is often referred to as "harpooning" (7). There are many studies of the orientation dependence of harpooning in gas-phase reactions (8, 9), but little is known about steric influences on ET reactions during molecule-surface scattering events. An influence of N 2 O orientation on exoelectron emission has been seen for reactions at alkali surfaces (10). Mechanistic studies revealed evidence for an Eley-Rideal reaction involving an ET event (11, 12). However, theoretical considerations suggest that the ET from the solid to N 2 O is independent of N 2 O orientation (13). To our knowledge, there is no unambiguous measurement of the orientation dependence of an ET reaction at a solid surface.We have found a unique way to measure the orientation dependence of a simple ET reaction occurring when ...

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“…If E → V transfer were to account for the discrepancy with experiment, at the E i corresponding to the gain peak (80 kJ∕mol) the probability for this process would have to be in the range 0.10-0.15 (30). The likelihood of such a probability can be assessed by considering recent experiments on vibrational excitation of NO scattering from Au(111) (31) and Cu (110) (32). The v ¼ 0 → 1 vibrational excitation energy of NO (23 kJ∕mol) is close to the frequency of the H 2 vibration near the barrier (which may be taken as approximately one half the vibrational quantum (19); i.e., as 25 kJ∕mol).…”

Section: Discussionmentioning

confidence: 99%

Apparent failure of the Born–Oppenheimer static surface model for vibrational excitation of molecular hydrogen on copper

Kroes

Dı́az

Pijper

et al. 2010

Proc. Natl. Acad. Sci. U.S.A.

109

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The accuracy of dynamical models for reactive scattering of molecular hydrogen, H 2 , from metal surfaces is relevant to the validation of first principles electronic structure methods for molecules interacting with metal surfaces. The ability to validate such methods is important to progress in modeling heterogeneous catalysis. Here, we study vibrational excitation of H 2 on Cu(111) using the Born-Oppenheimer static surface model. The potential energy surface (PES) used was validated previously by calculations that reproduced experimental data on reaction and rotationally inelastic scattering in this system with chemical accuracy to within errors ≤ 1 kcal∕mol ≈ 4.2 kJ∕mol [Díaz C, et al. (2009) Science 326:832-834]. Using the same PES and model, our dynamics calculations underestimate the contribution of vibrational excitation to previously measured time-of-flight spectra of H 2 scattered from Cu(111) by a factor 3. Given the accuracy of the PES for the experiments for which the Born-Oppenheimer static surface model is expected to hold, we argue that modeling the effect of the surface degrees of freedom will be necessary to describe vibrational excitation with similar high accuracy.Born-Oppenheimer approximation | dissociative chemisorption | molecule-surface scattering R eactions of molecules with metal surfaces are of tremendous importance, as the production of most man-made chemicals involves heterogeneous catalysis by a metal surface. One of the achievements recognized by the 2007 Nobel Prize in Chemistry, awarded to G. Ertl, was the detailed description of the sequence of elementary molecule-surface reactions by which ammonia is produced (1). In such reaction sequences, the dissociative chemisorption of molecules often plays a prominent role.In the present state of the art, theoretical calculations can reproduce overall rates of heterogeneously catalyzed reactions like ammonia production to within an order of magnitude (2). Achieving greater precision has been hampered by the lack of accuracy inherent in the density functional theory (DFT) used to calculate the interactions of molecules with metal surfaces.Because dissociative chemisorption involves stretching bonds until they rupture, reactivity of molecules on surfaces is closely related to transfer of energy to and from the vibrational degrees of freedom (3). Thus vibrationally inelastic scattering can be a sensitive probe of the barrier region of the potential energy surface (PES), and experiments (4, 5) and theory (6, 7) suggest that this process is governed by the same region of the PES as dissociative chemisorption: The picture of vibrational excitation occurring in competition with dissociative chemisorption is that it results from a stretching of the molecule as it approaches the transition state (4, 5). In principle, experiments on this competition may reveal much interesting information. For instance, comparison of data on vibrationally inelastic scattering and reaction on a surface has been suggested to provide information on whether these pro...

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Vibrational excitation of NO scattered from Cu(110)

Cited by 43 publications

References 21 publications

On the temperature dependence of electronically non-adiabatic vibrational energy transfer in molecule–surface collisions

On the temperature dependence of electronically non-adiabatic vibrational energy transfer in molecule–surface collisions

Observation of orientation-dependent electron transfer in molecule–surface collisions

Apparent failure of the Born–Oppenheimer static surface model for vibrational excitation of molecular hydrogen on copper

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