Water dissociation on Cu (111): Effects of molecular orientation, rotation, and vibration on reactivity

Mondal, Arobendo; Seenivasan, H.; Tiwari, Ashwani Kumar

doi:10.1063/1.4749246

Cited by 32 publications

(34 citation statements)

References 40 publications

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“…Earlier quantum dynamical studies on water dissociation on Cu(111) surface showed enhancement in reactivity with vibrational excitation. [18][19][20][21] Detailed quantum studies on mode selectivity in H 2 O dissociation on Cu(111) surface reported similar softening of symmetric stretching and bending modes, leading to enhancement in reactivity. 21 They attributed this increase to the "late" barrier for this reaction.…”

Section: E Transition State Geometries and Vibrational Frequenciesmentioning

confidence: 96%

“…19 In both cases, increase in reactivity is attributed to "late" barrier for reaction. Effect of molecular orientation, rotation, and vibration on water dissociation on Cu(111) surface on a low dimensional LEPS PES 20 and on a quasi-7-D PES 21 are also available in literature. These investigations illustrate the significance of excitation in orientational, rotational, and vibrational states on the dissociation probability in detail.…”

Section: Introductionmentioning

confidence: 99%

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Water dissociation on Ni(100) and Ni(111): Effect of surface temperature on reactivity

Seenivasan

Tiwari

2013

The Journal of Chemical Physics

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Water adsorption and dissociation on Ni(100) and Ni(111) surfaces are studied using density functional theory calculations. Water adsorbs on top site on both the surfaces, while H and OH adsorb on four fold hollow and three fold hollow (fcc) sites on Ni(100) and Ni(111), respectively. Transition states (TS) on both surfaces are identified using climbing image-nudged elastic band method. It is found that the barrier to dissociation on Ni(100) surface is slightly lower than that on Ni(111) surface. Dissociation on both the surfaces is exothermic, while the exothermicity on Ni(100) is large. To study the effect of lattice motion on the energy barrier, TS calculations are performed for various values of Q (lattice atom coordinate along the surface normal) and the change in the barrier height and position is determined. Calculations show that the energy barrier to reaction decreases with increasing Q and increases with decreasing Q on both the surfaces. Dissociation probability values at different surface temperatures are computed using semi-classical approximation. Results show that the influence of surface temperature on dissociation probability on the Ni(100) is significantly larger compared to that of Ni(111). Moreover, on Ni(100), a dramatic shift in energy barrier to lower incident energy values is observed with increasing surface temperature, while the shift is smaller in the case of Ni(111).

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Section: E Transition State Geometries and Vibrational Frequenciesmentioning

confidence: 96%

Section: Introductionmentioning

confidence: 99%

Water dissociation on Ni(100) and Ni(111): Effect of surface temperature on reactivity

Seenivasan

Tiwari

2013

The Journal of Chemical Physics

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“…We note in passing that similar mode specificity was observed by others using a much cruder model. 149 The strong mode specificity in these theoretical studies strongly suggests that the DC process is dominated by dynamics and different forms of energy have different efficacies in promoting the reaction. Subsequently, this 6D model was used to study bond selectivity in the DC of HOD.…”

Section: A H 2 Omentioning

confidence: 98%

Quantum dynamics of polyatomic dissociative chemisorption on transition metal surfaces: mode specificity and bond selectivity

et al. 2016

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Dissociative chemisorption is the initial and often rate-limiting step in many heterogeneous processes. As a result, an in-depth understanding of the reaction dynamics of such processes is of great importance for the establishment of a predictive model of heterogeneous catalysis. Overwhelming experimental evidence has suggested that these processes have a non-statistical nature and excitations in various reactant modes have a significant impact on reactivity. A comprehensive characterization of the reaction dynamics requires a quantum mechanical treatment on a global potential energy surface. In this review, we summarize recent progress in constructing high-dimensional potential energy surfaces for polyatomic molecules interacting with transition metal surfaces based on the plane-wave density functional theory and in quantum dynamical studies of dissociative chemisorption on these potential energy surfaces. A special focus is placed on the mode specificity and bond selectivity in these gas-surface collisional processes, and their rationalization in terms of the recently proposed Sudden Vector Projection model.

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“…43,44 Similar conclusions have been reached by others with a lower dimensional model. 45 This should not come as a surprise as H 2 O, like CH 4 , has slow IVR, 24 and its interaction with transition metal surfaces is also characterized by PESs with a "late" barrier. [46][47][48][49][50][51][52] Our theoretical model predicted that all three vibrational modes enhance the reactivity more efficiently than translational energy, underscoring their strong coupling with the reaction coordinate.…”

Section: Introductionmentioning

confidence: 99%

Effects of reactant internal excitation and orientation on dissociative chemisorption of H2O on Cu(111): Quasi-seven-dimensional quantum dynamics on a refined potential energy surface

Jiang

Xie

et al. 2013

The Journal of Chemical Physics

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To understand the influence of reactant internal excitation and orientation on the dissociative chemisorption of water on Cu(111), a quasi-seven-dimensional quantum dynamics study has been carried out on a refined potential energy surface (PES). The new PES was modified in the asymptotic region to allow an accurate characterization of the H(2)O ro-vibrational levels. The mode selectivity of the reaction was reexamined on the new PES and found to be consistent with our earlier work. To rationalize the observed mode selectivity, a vibrationally adiabatic reaction path model was determined on this PES. Furthermore, the reactivity for various rotationally excited H(2)O was investigated. It is shown that even low rotational excitation in H(2)O can either enhance or inhibit the reaction and the reactivity depends on the orientation of the impinging molecule.

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Water dissociation on Cu (111): Effects of molecular orientation, rotation, and vibration on reactivity

Cited by 32 publications

References 40 publications

Water dissociation on Ni(100) and Ni(111): Effect of surface temperature on reactivity

Water dissociation on Ni(100) and Ni(111): Effect of surface temperature on reactivity

Quantum dynamics of polyatomic dissociative chemisorption on transition metal surfaces: mode specificity and bond selectivity

Effects of reactant internal excitation and orientation on dissociative chemisorption of H2O on Cu(111): Quasi-seven-dimensional quantum dynamics on a refined potential energy surface

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