Effects of Strain on the Dissociation Dynamics of<mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML" display="inline"><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mn>2</mml:mn></mml:msub></mml:math>on Si(001)

Yata, Masanori; Uesugi-Saitow, Yuki; Kitajima, Masahiro; Kubo, Atsushi; Korsukov, V. E.

doi:10.1103/physrevlett.91.206103

Cited by 26 publications

(12 citation statements)

References 27 publications

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“…In this context, surface strain has been extensively investigated during last years [1][2][3][4][5][6][7][8][9][10][11][12]. Its practical realization can be achieved by the pseudomorphic growth of ultrathin metallic films on the surface of a different metal [1,5].…”

Section: Introductionmentioning

confidence: 99%

The dynamics of adsorption and dissociation of N₂ in a monolayer of iron on W(110)

Goikoetxea

Alducin

Muiño

et al. 2015

Phys. Chem. Chem. Phys.

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We study the adsorption dynamics of N2 on an expanded monolayer of Fe grown pseudomorphically on W(110). To this aim we have performed molecular dynamics simulations in a six-dimensional potential energy surface calculated within density functional theory. Our results show that N2 dissociation on this surface is a highly activated process with an energy barrier of around 1.25 eV. Regarding molecular adsorption, we find that the energetically most favorable adsorption well corresponds to a parallel orientation of the molecule with an adsorption energy of around 520 meV. However, at low molecular energies and surface temperatures, the molecules preferentially adsorb vertically to the surface with an adsorption energy of around 480 meV. A comparative analysis with the results previously obtained on a clean Fe(110) surface shows that while surface strain favors molecular adsorption of N2 in this system, it impedes dissociative adsorption. The former is consistent with the experimental observations showing that the inertness of Fe(110) towards N2 uptake is reduced in the strained surface. The latter leads us to suggest that the experimental observation of dissociated atomic N in the strained surface when increasing surface temperature must be related to the presence of step/defects at the surface.

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Section: Introductionmentioning

confidence: 99%

The dynamics of adsorption and dissociation of N₂ in a monolayer of iron on W(110)

Goikoetxea

Alducin

Muiño

et al. 2015

Phys. Chem. Chem. Phys.

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“…Second, it is based on arguments that do not to apply to transition metals with half-filled or fully filled d bands and such systems show important catalytic behavior. [9][10][11] Last but not least, the model is not applicable to non-transition-metal surfaces, some of them exhibiting important surface chemistry, [12][13][14] and also in systems where the s band may play an important role in chemical activity. 15 In the present work, we take an alternate view to elucidate the effect of strain on the adsorptive and catalytic properties of metal surfaces, based on linear elastic theory.…”

Section: Introductionmentioning

confidence: 99%

Determining the adsorptive and catalytic properties of strained metal surfaces using adsorption-induced stress

Pala

Liu²

2004

The Journal of Chemical Physics

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We demonstrate a model for determining the adsorptive and catalytic properties of strained metal surfaces based on linear elastic theory, using first-principles calculations of CO adsorption on Au and K surfaces and CO dissociation on Ru surface. The model involves a single calculation of the adsorption-induced surface stress on the unstrained metal surface, which determines quantitatively how adsorption energy changes with external strain. The model is generally applicable to both transition- and non-transition-metal surfaces, as well as to different adsorption sites on the same surface. Extending the model to both the reactant and transition state of surface reactions should allow determination of the effect of strain on surface reactivity.

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“…Chemical properties can be locally altered by several elements, including defects, steps, and/or other adsorbed species. Local strain at the surface has been also shown to change surface reactivity in a significant way [11,12]. However, tuning the adsorption properties in the extended surface is much more involved.…”

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confidence: 99%

Surface Strain Improves Molecular Adsorption but Hampers Dissociation forN2on theFe/W(
Goikoetxea
¹
,
Juaristi
²
,
Muiño
³

et al. 2014
Phys. Rev. Lett.
38
6
36
0
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We compare the adsorption dynamics of N 2 on the unstrained Fe(110) and on a 10% expanded Fe monolayer grown on W(110) by performing classical molecular dynamics simulations that use potential energy surfaces calculated with density functional theory. Our results allow us to understand why, experimentally, the molecular adsorption of N 2 is observed on the strained layer but not on Fe(110). Surprisingly, we also find that while surface strain favors the molecular adsorption of N 2 it seems, on the contrary, to impede the dissociative adsorption. This result contrasts with previous examples for which strain is found to modify equally the energetics of chemisorption and dissociation. DOI: 10.1103/PhysRevLett.113.066103 PACS numbers: 68.43.−h, 34.35.+a, 82.20.Kh, 82.65.+r The adsorption of nitrogen on iron surfaces is the standard textbook example when linking basic surface science and industrial heterogeneous catalysis [1]. N 2 adsorption and dissociation is the rate limiting step in ammonia synthesis and iron-based compounds are the preferred solid catalyzers for such a process. It is not a surprise then that extensive research has been devoted to understand and ameliorate the chemistry between N 2 and Fe surfaces [2][3][4][5][6][7][8][9][10]. Chemical properties can be locally altered by several elements, including defects, steps, and/or other adsorbed species. Local strain at the surface has been also shown to change surface reactivity in a significant way [11,12]. However, tuning the adsorption properties in the extended surface is much more involved. A clever way to do so is the pseudomorphic growth of ultrathin metallic films on top of substrates with different lattice constants. The electronic properties of the stretched (compressed) surface can be substantially modified giving rise to profound changes in the adsorption energetics between strained and unstrained surfaces [13][14][15][16][17][18][19][20]. Hitherto, all the studied systems show that the overall adsorption properties are equally altered, i.e., that the atomic, molecular, and dissociative adsorption are either all improved or all reduced.In the particular case of N 2 , it has been experimentally shown that the growth of Fe layers on W(110) strongly enhances the adsorption and dissociation of N 2 as compared with the otherwise fairly unreactive Fe(110) surface [6]. These observations agree with the above mentioned existing understanding of how surface strain affects the overall adsorption properties. However, we show here by means of molecular dynamics simulations that while surface strain favors molecular adsorption due to a uniform reduction of the energy barriers accessing the wells, its effect on the energetics of the dissociation process is surprisingly the opposite and, therefore, the observed atomic N cannot be directly attributed to surface strain in this case. We actually find that the minimum energy barrier to dissociation found in Fe(110) increases by about 500 meV in Fe=Wð110Þ. Interestingly, this energy upshift is not uniformly ...

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Effects of Strain on the Dissociation Dynamics ofO2on Si(001)

Cited by 26 publications

References 27 publications

The dynamics of adsorption and dissociation of N₂ in a monolayer of iron on W(110)

The dynamics of adsorption and dissociation of N₂ in a monolayer of iron on W(110)

Determining the adsorptive and catalytic properties of strained metal surfaces using adsorption-induced stress

Surface Strain Improves Molecular Adsorption but Hampers Dissociation forN2on theFe/W(
Goikoetxea
¹
,
Juaristi
²
,
Muiño
³

et al. 2014
Phys. Rev. Lett.
38
6
36
0
View full text Add to dashboard Cite

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Effects of Strain on the Dissociation Dynamics ofO2on Si(001)

Cited by 26 publications

References 27 publications

The dynamics of adsorption and dissociation of N2 in a monolayer of iron on W(110)

The dynamics of adsorption and dissociation of N2 in a monolayer of iron on W(110)

Determining the adsorptive and catalytic properties of strained metal surfaces using adsorption-induced stress

Surface Strain Improves Molecular Adsorption but Hampers Dissociation forN2on theFe/W(Goikoetxea1, Juaristi2, Muiño3 et al. 2014Phys. Rev. Lett.386360View full textAdd to dashboardCite

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The dynamics of adsorption and dissociation of N₂ in a monolayer of iron on W(110)

The dynamics of adsorption and dissociation of N₂ in a monolayer of iron on W(110)

Surface Strain Improves Molecular Adsorption but Hampers Dissociation forN2on theFe/W(
Goikoetxea
¹
,
Juaristi
²
,
Muiño
³

et al. 2014
Phys. Rev. Lett.
38
6
36
0
View full text Add to dashboard Cite