Incipient FeO(1 1 1) monolayer formation during O-adsorption on Fe(1 1 0) surface

Urslaan K. Chohan; Sven P.K. Koehler; Enrique Jimenez-Melero

doi:10.1016/j.commatsci.2017.03.033

Incipient FeO(1 1 1) monolayer formation during O-adsorption on Fe(1 1 0) surface

Urslaan K. Chohan^*, Sven P.K. Koehler, Enrique Jimenez-Melero

^*Corresponding author for this work

Metallurgy and Materials

Research output: Contribution to journal › Article › peer-review

Abstract

The adsorption of O atoms on the Fe(1 1 0) surface has been investigated by density functional theory for increasing degrees of oxygen coverage from 0.25 to 1 monolayer, to follow the evolution of the O[sbnd]Fe(1 1 0) system into an FeO(1 1 1)-like monolayer. We found that the quasi-threefold site is the most stable adsorption site for all coverages, with adsorption energies of ∼2.8–4.0 eV per O atom. Oxygen adsorption results in surface geometrical changes such as interlayer relaxation and buckling, the latter of which decreases with coverage. The calculated vibrational frequencies range from 265 to 470 cm⁻¹ for the frustrated translational modes and 480–620 cm⁻¹ for the stretching mode, and hence are in good agreement with the experimental values reported for bulk FeO wüstite. The hybridization of the oxygen 2p and iron 3d orbitals increases with oxygen coverage, and the partial density of states for the O[sbnd]Fe(1 1 0) system at full coverage resembles the one reported in the literature for bulk FeO. These results at full oxygen coverage point to the incipient formation of an FeO(1 1 1)-like monolayer that would eventually lead to the bulk FeO oxide layer.

Original language	English
Pages (from-to)	109-115
Number of pages	7
Journal	Computational Materials Science
Volume	134
DOIs	https://doi.org/10.1016/j.commatsci.2017.03.033
Publication status	Published - 15 Jun 2017

Bibliographical note

Funding Information:
We gratefully acknowledge the financial support of the Engineering and Physical Sciences Research Council UK (EPSRC) through the Centre for Doctoral Training in Advanced Metallic Systems (EP/L016273/1). We also thank the Dalton Cumbrian Facility, partly funded by the Nuclear Decommissioning Authority, for providing funding to cover the cost of computational time.

Publisher Copyright:
© 2017 Elsevier B.V.

Keywords

Chemisorption
Density functional theory
Ferrite
Oxidation
Partial density of states
Surface relaxation

ASJC Scopus subject areas

General Computer Science
General Chemistry
General Materials Science
Mechanics of Materials
General Physics and Astronomy
Computational Mathematics

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10.1016/j.commatsci.2017.03.033

Cite this

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title = "Incipient FeO(1 1 1) monolayer formation during O-adsorption on Fe(1 1 0) surface",

abstract = "The adsorption of O atoms on the Fe(1 1 0) surface has been investigated by density functional theory for increasing degrees of oxygen coverage from 0.25 to 1 monolayer, to follow the evolution of the O[sbnd]Fe(1 1 0) system into an FeO(1 1 1)-like monolayer. We found that the quasi-threefold site is the most stable adsorption site for all coverages, with adsorption energies of ∼2.8–4.0 eV per O atom. Oxygen adsorption results in surface geometrical changes such as interlayer relaxation and buckling, the latter of which decreases with coverage. The calculated vibrational frequencies range from 265 to 470 cm−1 for the frustrated translational modes and 480–620 cm−1 for the stretching mode, and hence are in good agreement with the experimental values reported for bulk FeO w{\"u}stite. The hybridization of the oxygen 2p and iron 3d orbitals increases with oxygen coverage, and the partial density of states for the O[sbnd]Fe(1 1 0) system at full coverage resembles the one reported in the literature for bulk FeO. These results at full oxygen coverage point to the incipient formation of an FeO(1 1 1)-like monolayer that would eventually lead to the bulk FeO oxide layer.",

keywords = "Chemisorption, Density functional theory, Ferrite, Oxidation, Partial density of states, Surface relaxation",

author = "Chohan, {Urslaan K.} and Koehler, {Sven P.K.} and Enrique Jimenez-Melero",

note = "Funding Information: We gratefully acknowledge the financial support of the Engineering and Physical Sciences Research Council UK (EPSRC) through the Centre for Doctoral Training in Advanced Metallic Systems (EP/L016273/1). We also thank the Dalton Cumbrian Facility, partly funded by the Nuclear Decommissioning Authority, for providing funding to cover the cost of computational time. Publisher Copyright: {\textcopyright} 2017 Elsevier B.V.",

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doi = "10.1016/j.commatsci.2017.03.033",

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AU - Chohan, Urslaan K.

AU - Koehler, Sven P.K.

AU - Jimenez-Melero, Enrique

N1 - Funding Information: We gratefully acknowledge the financial support of the Engineering and Physical Sciences Research Council UK (EPSRC) through the Centre for Doctoral Training in Advanced Metallic Systems (EP/L016273/1). We also thank the Dalton Cumbrian Facility, partly funded by the Nuclear Decommissioning Authority, for providing funding to cover the cost of computational time. Publisher Copyright: © 2017 Elsevier B.V.

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Y1 - 2017/6/15

N2 - The adsorption of O atoms on the Fe(1 1 0) surface has been investigated by density functional theory for increasing degrees of oxygen coverage from 0.25 to 1 monolayer, to follow the evolution of the O[sbnd]Fe(1 1 0) system into an FeO(1 1 1)-like monolayer. We found that the quasi-threefold site is the most stable adsorption site for all coverages, with adsorption energies of ∼2.8–4.0 eV per O atom. Oxygen adsorption results in surface geometrical changes such as interlayer relaxation and buckling, the latter of which decreases with coverage. The calculated vibrational frequencies range from 265 to 470 cm−1 for the frustrated translational modes and 480–620 cm−1 for the stretching mode, and hence are in good agreement with the experimental values reported for bulk FeO wüstite. The hybridization of the oxygen 2p and iron 3d orbitals increases with oxygen coverage, and the partial density of states for the O[sbnd]Fe(1 1 0) system at full coverage resembles the one reported in the literature for bulk FeO. These results at full oxygen coverage point to the incipient formation of an FeO(1 1 1)-like monolayer that would eventually lead to the bulk FeO oxide layer.

AB - The adsorption of O atoms on the Fe(1 1 0) surface has been investigated by density functional theory for increasing degrees of oxygen coverage from 0.25 to 1 monolayer, to follow the evolution of the O[sbnd]Fe(1 1 0) system into an FeO(1 1 1)-like monolayer. We found that the quasi-threefold site is the most stable adsorption site for all coverages, with adsorption energies of ∼2.8–4.0 eV per O atom. Oxygen adsorption results in surface geometrical changes such as interlayer relaxation and buckling, the latter of which decreases with coverage. The calculated vibrational frequencies range from 265 to 470 cm−1 for the frustrated translational modes and 480–620 cm−1 for the stretching mode, and hence are in good agreement with the experimental values reported for bulk FeO wüstite. The hybridization of the oxygen 2p and iron 3d orbitals increases with oxygen coverage, and the partial density of states for the O[sbnd]Fe(1 1 0) system at full coverage resembles the one reported in the literature for bulk FeO. These results at full oxygen coverage point to the incipient formation of an FeO(1 1 1)-like monolayer that would eventually lead to the bulk FeO oxide layer.

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