scholarly journals Spin-density functional theories and their+Uand+Jextensions: A comparative study of transition metals and transition metal oxides

2016 ◽  
Vol 93 (4) ◽  
Author(s):  
Hanghui Chen ◽  
Andrew J. Millis
Keyword(s):  
Transition Metal ◽  
Transition Metals ◽  
Comparative Study ◽  
Metal Oxides ◽  
Spin Density ◽  
Transition Metal Oxides ◽  
Density Functional

Transition Metal Oxide-Diamond Interfaces for Electron Emission Applications

2013 ◽  
Vol 740-742 ◽  
pp. 761-764
Author(s):  
Amit K. Tiwari ◽  
Jonathan P. Goss ◽  
Patrick R. Briddon ◽  
Nicholas G. Wright ◽  
Alton B. Horsfall ◽  
...  
Keyword(s):  
Transition Metal ◽  
Transition Metals ◽  
Metal Oxides ◽  
Electron Affinity ◽  
Transition Metal Oxides ◽  
Density Functional ◽  
Chemical Species ◽  
Negative Electron Affinity ◽  
Diamond Surfaces ◽  
Electron Emitters

Diamond surfaces with suitable adsorbed chemical species can exhibit both negative and positive electron affinities, arising from the complex electrostatic interplay between adsorbates and surface carbon atoms of diamond lattice. We presents the results of density functional calculations into the energetics and the electron affinity of diamond (100) surfaces terminated with the oxides of selected transition metals. We find that for a correct stoichiometry, oxides of transition metals, such as Ti and Zn, exhibit a large negative electron affinity of around 3 eV. The desorption of transition metal oxides is found to be highly endothermic. We therefore propose that transition metal oxides are promising for the surface coating of diamond-based electron emitters, as these exhibit higher thermal stability in comparison to the commonly used CsO terminations, while retaining the advantage of inducing a large negative electron affinity.

scholarly journals Stable Surfaces that Bind too Tightly: Can Range Separated Hybrids or DFT+U Improve Paradoxical Descriptions of Surface Chemistry?

2019 ◽  
Author(s):  
Qing Zhao ◽  
Heather Kulik
Keyword(s):  
Transition Metal ◽  
Transition Metals ◽  
Metal Oxides ◽  
Transition Metal Oxides ◽  
Density Functional ◽  
Local Density ◽  
Computational Cost ◽  
Hartree Fock ◽  
Hybrid Functionals ◽  
Local Range

Approximate, semi-local density functional theory (DFT) suffers from delocalization error that can lead to a paradoxical overbinding of surface adsorbates and overestimation of surface stabilities in catalysis modeling. We investigate the effect of two widely applied approaches for delocalization error correction, i) affordable DFT+U (i.e., semi-local DFT augmented with a Hubbard U) and ii) hybrid functionals with an admixture of Hartree-Fock (HF) exchange, on surface and adsorbate energies across a range of rutile transition metal oxides widely studied for their promise as water splitting catalysts. We observe strongly row- and period-dependent trends with DFT+U, which increases surface formation energies only in early transition metals (e.g., Ti, V) and decreases adsorbate energies only in later transition metals (e.g., Ir, Pt). Both global and local hybrids destabilize surfaces and reduce adsorbate binding across the periodic table, in agreement with higher-level reference calculations. Density analysis reveals why hybrid functionals correct both quantities, whereas DFT+U does not. We recommend local, range-separated hybrids for the accurate modeling of catalysis in transition metal oxides at only a modest increase in computational cost over semi-local DFT.

scholarly journals Stable Surfaces that Bind too Tightly: Can Range Separated Hybrids or DFT+U Improve Paradoxical Descriptions of Surface Chemistry?

2019 ◽  
Author(s):  
Qing Zhao ◽  
Heather Kulik
Keyword(s):  
Transition Metal ◽  
Transition Metals ◽  
Metal Oxides ◽  
Transition Metal Oxides ◽  
Density Functional ◽  
Local Density ◽  
Computational Cost ◽  
Hartree Fock ◽  
Hybrid Functionals ◽  
Local Range

Approximate, semi-local density functional theory (DFT) suffers from delocalization error that can lead to a paradoxical overbinding of surface adsorbates and overestimation of surface stabilities in catalysis modeling. We investigate the effect of two widely applied approaches for delocalization error correction, i) affordable DFT+U (i.e., semi-local DFT augmented with a Hubbard U) and ii) hybrid functionals with an admixture of Hartree-Fock (HF) exchange, on surface and adsorbate energies across a range of rutile transition metal oxides widely studied for their promise as water splitting catalysts. We observe strongly row- and period-dependent trends with DFT+U, which increases surface formation energies only in early transition metals (e.g., Ti, V) and decreases adsorbate energies only in later transition metals (e.g., Ir, Pt). Both global and local hybrids destabilize surfaces and reduce adsorbate binding across the periodic table, in agreement with higher-level reference calculations. Density analysis reveals why hybrid functionals correct both quantities, whereas DFT+U does not. We recommend local, range-separated hybrids for the accurate modeling of catalysis in transition metal oxides at only a modest increase in computational cost over semi-local DFT.

scholarly journals Determination of Formation Energies and Phase Diagrams of Transition Metal Oxides with DFT+U

Materials ◽  
2020 ◽  
Vol 13 (19) ◽  
pp. 4303
Author(s):  
Daniel Mutter ◽  
Daniel F. Urban ◽  
Christian Elsässer
Keyword(s):  
Transition Metal ◽  
Metal Oxides ◽  
Phase Diagrams ◽  
Transition Metal Oxides ◽  
Density Functional ◽  
Synthesis Process ◽  
Local Exchange ◽  
Electronic Band ◽  
Formation Energies

Knowledge about the formation energies of compounds is essential to derive phase diagrams of multicomponent phases with respect to elemental reservoirs. The determination of formation energies using common (semi-)local exchange-correlation approximations of the density functional theory (DFT) exhibits well-known systematic errors if applied to oxide compounds containing transition metal elements. In this work, we generalize, reevaluate, and discuss a set of approaches proposed and widely applied in the literature to correct for errors arising from the over-binding of the O2 molecule and from correlation effects of electrons in localized transition-metal orbitals. The DFT+U method is exemplarily applied to iron oxide compounds, and a procedure is presented to obtain the U values, which lead to formation energies and electronic band gaps comparable to the experimental values. Using such corrected formation energies, we derive the phase diagrams for LaFeO3, Li5FeO4, and NaFeO2, which are promising materials for energy conversion and storage devices. A scheme is presented to transform the variables of the phase diagrams from the chemical potentials of elemental phases to those of precursor compounds of a solid-state reaction, which represents the experimental synthesis process more appropriately. The discussed workflow of the methods can directly be applied to other transition metal oxides.

FACILE CYCLOADDITION OF TRANSITION METAL OXIDES ONTO THE SIDEWALL OF BORON-DOPED FULLERENE

2009 ◽  
Vol 16 (04) ◽  
pp. 525-532
Author(s):  
ZI-RONG TANG
Keyword(s):  
Transition Metal ◽  
Metal Oxides ◽  
Transition Metal Oxides ◽  
Density Functional ◽  
Density Functional Theory Calculations ◽  
Boron Doping ◽  
Organic Base ◽  
Functional Theory ◽  
Boron Doped ◽  
Ruthenium Tetraoxide

The viability of facile oxidation and cycloaddition of fullerene C 60 with ruthenium tetraoxide ( RuO 4) has been confirmed by means of density functional theory calculations. Owing to the powerful capability of RuO 4 as an oxidant, the addition process has been found to occur readily in the absence of organic base as a catalyst, which is in remarkable contrast to the base-catalyzed osmylation of C 60 with osmium tetraoxide ( OsO 4). Significantly, we have found that boron can be employed as an effective promoter for enhancing the cycloaddition and complexation of transition metal oxides, e.g. RuO 4 and OsO 4, with C 60, in which the base is not needed at all. Our results suggest that boron doping into the lattice of fullerenes and carbon nanotubes would provide a well-defined approach for anchoring transition metal oxides.

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