Theoretical treatment of excited electronic states of adsorbates on metals: Electron attachment to CO2 adsorbed on K-modified Pt(111)

Sremaniak, Laura S.; Whitten, J. L.

doi:10.1016/j.susc.2007.11.029

Cited by 6 publications

(4 citation statements)

References 21 publications

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“…Theoretical treatment of CO 2 adsorbed on K-modified Pt(111) (a surface with an electronic structure similar to Mo 2 C) reported by Sremainak and Whitten presents similar results. The most favorable pathway leading to dissociation requires that CO 2 be adsorbed at a site that does not share Pt atoms with the K adsorption site, that is, at next-nearest neighbor sites (as 3F2 site in our work).…”

Section: Resultssupporting

confidence: 72%

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Theoretical Model for CO Adsorption and Dissociation on Clean and K-Doped β-Mo₂C Surfaces

et al. 2012

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We studied the effect of K on the adsorption and dissociation of CO on the β-Mo2C (001) surface by density functional theory calculations. Molecular CO adsorbs more strongly on Mo-terminated surfaces than on C-terminated ones. Adsorption is energetically more favorable in the presence of preadsorbed potassium. The CO molecule withdraws electron density from the surface, being more extended on the K-doped surface. The CO dissociation was also evaluated, and reaction pathways were modeled, revealing that the C-terminated surface is energetically less favorable than the Mo-terminated one. For both surfaces, the activation energy barrier for dissociation increases with the K content. C–O vibrational frequencies were also computed on K-modified surfaces.

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Section: Resultssupporting

confidence: 72%

“…The use of atoms to model the effect of alkali additives is a common approach in DFT calculations and has been discussed in detail. ,− …”

Section: Computational Methods and Surface Modelsmentioning

confidence: 99%

Theoretical Model for CO Adsorption and Dissociation on Clean and K-Doped β-Mo₂C Surfaces

et al. 2012

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“…A small cluster is modeled using a high-level method, and then in a second step, this calculation is corrected for periodicity effects induced by the extended surface, calculated at a lower level of theory. Such approaches were already suggested in the 1970s and have been very popular in biochemistry for the modeling of zeolites as well as for metals. − One of the most popular methods is the ONIOM approach in which the whole system is initially modeled at a lower level of theory. A small cluster surrounding the active site of interest is then cut out and modeled with both low-level and high-level methods.…”

Section: Introductionmentioning

confidence: 99%

Importance of a Nonlocal Description of Electron–Electron Interactions in Modeling the Dissociative Adsorption of H₂ on Cu(100)

et al. 2014

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Describing the dissociation of molecules on metal surfaces is of major importance in understanding processes such as corrosion or heterogeneous catalysis. Because of its high efficiency and reasonable accuracy, density functional theory (DFT) is the method of choice in this field nowadays, but it can be expected that the semilocal treatment of the exchange-correlation introduces fundamental errors. To understand those errors, it is possible to reduce the complexity of the problem to, for example, describe the dissociation of H 2 on Cu(100). In this work, we model this process for an embedded, metallic cluster comparing coupled cluster, configuration interaction, and semilocal DFT calculations. We calculate a two-dimensional potential energy surface (PES) and identify the minimum energy pathway (MEP) for dissociation, the transition state, and also the dissociation minimum. Compared to DFT calculations, the interactions between the molecule and the surface are far more long ranged in explicitly correlated methods, and the dissociation is also far more exothermic. To accurately describe dissociation, it is necessary to take the multideterminant nature of the wave function in embedded MRCI+Q calculations into account. For them, we find excellent agreement with experiment. On the basis of these calculations, we discuss the reasons for shortcomings of semilocal density functionals described in recent literature. These results clearly show that an accurate nonlocal treatment of the electron−electron interactions qualitatively changes the potential energy surface for molecules interacting with extended systems and possibly improves agreement with experiments. It will be interesting to see how they can be transferred to and affect more complex problems such as modeling entire reaction pathways.

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“…Numerous investigations and studies had been carried out on this phenomenon, but the structure of Pt-HCOO was not consistent and had been the subject of controversy [3][4][5][6][7][8][9][10][11][12]. According to the results obtained with various nonelectrochemical techniques (IR, mass spectrometry, radiochemical methods), the following structures of the Pt-HCOO radicals were proposed: -COOH [5][6][7]13,14], -COH [8,9,14], -HCO [12], linearly or bridged bonded -CO [11,[15][16][17][18]. The investigation of the mechanism and the Pt-HCOO radicals are beyond the scope of this work.…”

Section: Introductionmentioning

confidence: 99%

Thick-film Carbon Dioxide Sensor via Anodic Adsorbate Stripping Technique and its Structural Dependence

Photinon¹,

Liu²

2008

Meet. Abstr.

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A three-electrode based CO 2 sensor was fabricated using thick-film technology. The performance of this sensor was further enhanced by incorporating platinum nanoparticles onto the working electrode surface. An eight-fold increase in the signal output was obtained from the electrode with the platinum nanoparticles. The sensing output was linearly related to the CO 2 presented. Stability measurements demonstrated that the decline of the active surface area and the sensitivity of the sensor were 8% and 13%, respectively, over a two week period of time. The sensor response appeared to be a structural dependence of the crystallographic orientation of platinum electrode.

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Theoretical treatment of excited electronic states of adsorbates on metals: Electron attachment to CO2 adsorbed on K-modified Pt(111)

Cited by 6 publications

References 21 publications

Theoretical Model for CO Adsorption and Dissociation on Clean and K-Doped β-Mo₂C Surfaces

Theoretical Model for CO Adsorption and Dissociation on Clean and K-Doped β-Mo₂C Surfaces

Importance of a Nonlocal Description of Electron–Electron Interactions in Modeling the Dissociative Adsorption of H₂ on Cu(100)

Thick-film Carbon Dioxide Sensor via Anodic Adsorbate Stripping Technique and its Structural Dependence

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Theoretical treatment of excited electronic states of adsorbates on metals: Electron attachment to CO2 adsorbed on K-modified Pt(111)

Cited by 6 publications

References 21 publications

Theoretical Model for CO Adsorption and Dissociation on Clean and K-Doped β-Mo2C Surfaces

Theoretical Model for CO Adsorption and Dissociation on Clean and K-Doped β-Mo2C Surfaces

Importance of a Nonlocal Description of Electron–Electron Interactions in Modeling the Dissociative Adsorption of H2 on Cu(100)

Thick-film Carbon Dioxide Sensor via Anodic Adsorbate Stripping Technique and its Structural Dependence

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Resources

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Theoretical Model for CO Adsorption and Dissociation on Clean and K-Doped β-Mo₂C Surfaces

Theoretical Model for CO Adsorption and Dissociation on Clean and K-Doped β-Mo₂C Surfaces

Importance of a Nonlocal Description of Electron–Electron Interactions in Modeling the Dissociative Adsorption of H₂ on Cu(100)