First-principles insights into the structure of the incipient magnesium oxide and its instability to decomposition: Oxygen chemisorption to Mg(0001) and thermodynamic stability

Francis, Michael F; Taylor, Christopher D.

doi:10.1103/physrevb.87.075450

Cited by 44 publications

(30 citation statements)

References 61 publications

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“…This is consistent with the experimental findings which suggest the formation of thin-dense MgO and thickporous Mg(OH)2 films from the occurrence of both partial and complete water-splitting reactions 34,66,[126][127][128][129][130] . As water molecule dissociates and oxygen adsorbs on the surface, crystalline MgO nucleates and grows laterally forming an oxide-cluster, followed by the precipitation and thickening process 145,146 . At later stages, because of the continuous hydration on the surface, crystalline MgO experiences severe breakdown (volume expansion) forming Mg(OH)2 via the dissolution-precipitation reactions 131 .…”

Section: Formation Of Oxide and Hydroxide Film On The Mg Surfacementioning

confidence: 99%

Aqueous electrochemistry of the magnesium surface: Thermodynamic and kinetic profiles

et al. 2019

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In this study, first-principles density functional theory (DFT) calculations are performed to investigate the contribution of each individual reaction at the magnesium/water interface. Thermodynamic and kinetic models derived from the DFT-calculated parameters are used to describe interdependent reactions at the interface and the resultant magnesium electrochemical activity at different pH and potentials. These models are able to rationalise experimental findings, such as those obtained from polarisation and immersion tests, and provide new insights for defining a complete and viable mechanism of aqueous magnesium electrochemistry.

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Section: Formation Of Oxide and Hydroxide Film On The Mg Surfacementioning

confidence: 99%

Aqueous electrochemistry of the magnesium surface: Thermodynamic and kinetic profiles

et al. 2019

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“…Recent adsorption studies of O on Mg(0001) [5] show the appearance of attractive interactions between chemisorbed oxygen atoms, which cannot be rationalized by the above scenarios and lead to a spinodal decomposition of surface phases at incomplete coverage. Employing firstprinciples total energy calculations together with a detailed bonding analysis, we show in the present study that attractive interactions between negatively charged adsorbates can occur and actually appear to be a common feature when second row electronegative elements are adsorbed on Mg(0001).…”

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confidence: 91%

“…There is, however, a pronounced interest in utilizing this low corrosion resistance for medical applications [3], due to the high biocompatibility of the material. Gaining a better understanding of the mechanisms governing the corrosion behavior of Mg is desirable in either case.Adsorption studies can give insight into the initial stages of the formation of corrosion products [4,5], which appear as a consequence of a substrate's interaction with its environment. A first quantum-mechanical explanation of adsorbate-substrate interactions and work function change was given by Gurney [6].…”

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Negatively Charged Ions on Mg(0001) Surfaces: Appearance and Origin of Attractive Adsorbate-Adsorbate Interactions

et al. 2014

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Adsorption of electronegative elements on a metal surface usually leads to an increase in the work function and decrease in the binding energy as the adsorbate coverage rises. Using density-functional theory calculations, we show that Cl adsorbed on a Mg(0001) surface complies with these expectations, but adsorption of {N,O,F} causes a decrease in the work function and an increase in the binding energy. Analyzing the electronic structure, we show that the presence of a highly polarizable electron spill-out in front of Mg(0001) causes this unusual adsorption behavior and is responsible for the appearance of a hitherto unknown net-attractive lateral electrostatic interaction between same charged adsorbates.

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“…48 The gradual evolution of the Ni 2+ charge state was monitored as a function of the extent of this initial oxidation. [49][50][51] Molecular dynamics simulations based upon the use of classical interatomic potentials have been performed for studying the passivation of metals including nickel, iron, aluminum, and zirconium. The oxidation of nickel was observed to proceed first by a gradual filling of the first monolayer of the surface with oxygen, and then by a reconstructed layer that created a mixed Ni-O-Ni bilayer.…”

Section: Understanding Passivity By Modeling Metal/metal-oxide Interfmentioning

confidence: 99%

Modeling Corrosion, Atom by Atom

Taylor¹

2014

Interface magazine

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I n the late 20 th century, computer programs emerged that could solve the fundamental quantum mechanical equations that control the interactions of atoms that give rise to bonding. These tools, first applied to molecules and bulk solid materials, then began to be applied to surfaces and, in the early 21 st century, to electrochemical environments. 1 Commercial and open-source programs are now readily available and can be used on both desktop and highperformance computing platforms to solve for the electronic structure of a given configuration of atomic centers (nuclei) and, in so doing, provide the basis for determining a whole host of properties, including electronic and vibrational spectra, electrical moments such as the system dipole, and, most importantly, the energy and forces on the atoms. 2-4 Other derived properties include the extent to which each atom is charged and bond-orders, although to compute these latter properties one of a variety of methods for dividing up and quantifying the electron density associated with each atom must be selected. 5 The physics behind these codes is complex, and, challengingly, has no rigorous analytical solution that can be obtained within a finite allotment of time. Thus, the computer programs themselves take advantage of approximations that allow for a feasible solution but, at the same time, constrain the accuracy of the result. Nonetheless, solutions can usually be reliably obtained for model systems representing materials, interfaces, or molecules that do not exceed thousands, and, more realistically, hundreds of atoms. 6 Given that system sizes of hundreds or thousands of atoms amount to no more than the smallest nanoparticle of a substance, the question arises: What can atomistic simulations teach us about corrosion?The answer to this question lies in the ability for atomistic simulation to confirm or deny key hypotheses associated with potential corrosion mechanisms. By directly simulating the structure of a molecule, its spectroscopic signatures, or the energetics of the bond-making and bond-breaking processes it engages in, much information can be gained that is useful to the interpretation of experiment and the verification of proposed theories. For instance, if a certain mechanistic step has a considerably large activation barrier (as computed from quantum mechanics), we can assume that it will not proceed unless somehow catalyzed. Furthermore, if a given atomic configuration is found to be metastable through molecular simulation, then we can predict that, over time, it will decay to a lower energy state. Furthermore, using periodic boundary conditions, it is possible to mimic the effects of semi-infinite surfaces (thus effectively going beyond the hundreds or thousands of atoms limit), albeit ensuring that careful attention is paid to address spurious results that may arise from image-image interactions.In this report we give several examples. In the first case we show how the computation of the properties of molecular systems can provide some insight as to ...

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First-principles insights into the structure of the incipient magnesium oxide and its instability to decomposition: Oxygen chemisorption to Mg(0001) and thermodynamic stability

Cited by 44 publications

References 61 publications

Aqueous electrochemistry of the magnesium surface: Thermodynamic and kinetic profiles

Aqueous electrochemistry of the magnesium surface: Thermodynamic and kinetic profiles

Negatively Charged Ions on Mg(0001) Surfaces: Appearance and Origin of Attractive Adsorbate-Adsorbate Interactions

Modeling Corrosion, Atom by Atom

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