Density Functional Theory Beyond the Generalized Gradient Approximation for Surface Chemistry

Janesko, Benjamin G.

doi:10.1007/128_2014_555

Cited by 13 publications

(5 citation statements)

References 291 publications

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“…A literature survey on more recent works using standard GGA PW91 30 and PBE 31 functionals and meta-GGA, PKZB, 32 RPBE 33 approximations reveal that the exact adsorption energy on particular sites depends heavily on the choice of the exchange-correlation functional. 14,34,35 Modern functionals tend to yield a consistent relative energy between adsorption energies at different sites, in agreement with a number of experimental parameters such as vibrational frequencies and work function changes for CO adsorption. 14 To explore the dissociation, the nudged elastic band (NEB) 36 method with PBE-GGA exchange-correlation functional has proven to be a reliable tool that can predict the minimumenergy reaction path.…”

Section: Introductionsupporting

confidence: 74%

Influence of surface vacancy defects on the carburisation of Fe 110 surface by carbon monoxide

Chakrabarty

Bouhali

Mousseau

et al. 2016

The Journal of Chemical Physics

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Adsorption and dissociation of gaseous carbon monoxide (CO) on metal surfaces is one of the most frequently occurring processes of carburisation, known as primary initiator of metal dusting corrosion. Among the various factors that can significantly influence the carburisation process are the intrinsic surface defects such as single surface vacancies occurring at high concentrations due to their low formation energy. Intuitively, adsorption and dissociation barriers of CO are expected to be lowered in the vicinity of a surface vacancy, due to the strong attractive interaction between the vacancy and the C atom. Here the adsorption energies and dissociation pathways of CO on clean and defective Fe 110 surface are explored by means of density functional theory. Interestingly, we find that the O adatom, resulting from the CO dissociation, is unstable in the electron-deficit neighbourhood of the vacancy due to its large electron affinity, and raises the barrier of the carburisation pathway. Still, a full comparative study between the clean surface and the vacancy-defected surface reveals that the complete process of carburisation, starting from adsorption to subsurface diffusion of C, is more favourable in the vicinity of a vacancy defect.

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Section: Introductionsupporting

confidence: 74%

Influence of surface vacancy defects on the carburisation of Fe 110 surface by carbon monoxide

Chakrabarty

Bouhali

Mousseau

et al. 2016

The Journal of Chemical Physics

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“…Pure functionals in Table show noticeably small values of the FS error regardless of rung. This explains their (relatively) good performance in solids. − Among the hybrids only TPSSh and HSE06 have relatively small FS errors. LC-PBETPSS and LC-ωPBE reverse the curvature of the FC error, thus showing too much of a HF behavior.…”

Section: Resultsmentioning

confidence: 95%

Assessment of Newest Meta-GGA Hybrids for Late Transition Metal Reactivity: Fractional Charge and Fractional Spin Perspective

2018

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In recent years there has been a significant interest of DFT community in the development of new (hybrid) meta-generalized gradient approximations (meta-GGAs), including range-separated hybrids. The new DFT methods, e.g., SCAN, SCAN0, ωB97M-V, and our own LC-PBETPSS-D3 promise an improvement over well-established models, such as, PBE, PBE0, ωB97X-D, and the M06-type functionals. However, the tests published to date cover only main-group chemistry. This work fills this gap by examining reactivity of model systems, such as gold-ligand complexes, Pd and Ni insertion reactions into covalent bonds, and the pathway for olefin metathesis by a model Grubbs system, all of which include late transition metals. In the attempt to rationalize the performance of functionals, we study the fractional charge and fractional spin errors of the Au atom and the Au7 cluster. While we find the main qualitative issues of DFT are not yet solved, the introduction of meta-GGA ingredients yields a notable improvement makeing the new meta-GGAs the preferred choice for transition-metal chemistry.

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“…The meta-GGA TPSS (Tao, Perdew, Staroverov, Scuseria) 53 functional was also used to obtain a comparison in the description of surface chemistry with the more broadly used and more validated PBE functional. 21,56 The comparison is provided in the ESI. † Since we are interested in the supramolecular assemblies that this molecules form over a surface, the inclusion of dispersion interactions is fundamental to accurately describe the non-covalent interaction between the macrocycle and the Au(111) surface.…”

Section: Theoretical and Computational Detailsmentioning

confidence: 99%

Theoretical exploration of the forces governing the interaction between gold–phthalocyanine and gold surface clusters

2020

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Density Functional Theory Beyond the Generalized Gradient Approximation for Surface Chemistry

Cited by 13 publications

References 291 publications

Influence of surface vacancy defects on the carburisation of Fe 110 surface by carbon monoxide

Influence of surface vacancy defects on the carburisation of Fe 110 surface by carbon monoxide

Assessment of Newest Meta-GGA Hybrids for Late Transition Metal Reactivity: Fractional Charge and Fractional Spin Perspective

Theoretical exploration of the forces governing the interaction between gold–phthalocyanine and gold surface clusters

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