Relativistic effects in structural chemistry

Pyykkö, Pekka

doi:10.1021/cr00085a006

Cited by 2,858 publications

(2,069 citation statements)

References 38 publications

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“…For Au 4 , the relativistic contraction of the Au 6s shell restores some s-d mixing and contributes to stronger M-M interactions between the gold atoms. [15,26] For each coinage metal tetramer, we considered three different configurations on the MgOA C H T U N G T R E N N U N G (001) surface: two upright structures, where the M 4 rhombus is attached to the substrate by two ( Figure 1, mode A) or one atom M (mode B) and a moiety oriented parallel to the surface (mode C). In contrast to the lowest-energy structures A, structures B and C appear to be a local minimum only under C 2v symmetry constraints.…”

Section: Resultsmentioning

confidence: 99%

Density Functional Embedded Cluster Study of Cu₄, Ag₄ and Au₄ Species Interacting with Oxygen Vacancies on the MgO(001) Surface

Neyman

Inntam

Moskaleva

et al. 2006

Chemistry A European J

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Cu4, Ag4, and Au4 species adsorbed on an MgO(001) surface that exhibits neutral (Fs) and charged (Fs+) oxygen vacancies have been studied using a density functional approach and advanced embedding models. The gas‐phase rhombic‐planar structure of the coinage metal tetramers is only moderately affected by adsorption. In the most stable surface configuration, the plane of the tetramers is oriented perpendicular to the MgO(001) surface; one metal atom is attached to an oxygen vacancy and another one is bound to a nearby surface oxygen anion. A very similar structural motif was recently found on defect‐free MgO(001), where two O2− ions serve as adsorption sites. Following the trend of the interactions with the regular MgO(001) surface, Au4 and Cu4 bind substantially stronger to Fs and Fs+ sites than Ag4. This stronger adsorption interaction at oxygen vacancies, in particular at Fs, is partly due to a notable accumulation of electron density on the adsorbates. We also examined the propensity of small supported metal species to aggregate to adsorbed di‐, tri‐ and tetramers. Furthermore, we demonstrated that core‐level ionization potentials offer the possibility for detecting experimentally supported metal tetramers and characterizing them structurally with the help of calculated data.

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Section: Resultsmentioning

confidence: 99%

Density Functional Embedded Cluster Study of Cu₄, Ag₄ and Au₄ Species Interacting with Oxygen Vacancies on the MgO(001) Surface

Neyman

Inntam

Moskaleva

et al. 2006

Chemistry A European J

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“…The Swart-Solá-Bickelhaupt (SSB-D) functional 53,54 , was constructed on the basis of a small correction of the PBE functional, together with Grimme's dispersion correction and it was shown to work well for spin states of transition metal complexes, S N 2 reaction barriers, accuracy of geometries, hydrogen bonding, and π − π stacking interactions. One of the most important factors for a correct description of heavy transition metals such as Pt is undoubtedly relativistic effects [55][56][57][58] . An accurate way to include relativistic effects is to use the full four-component Dirac equation 59 , however the application of such approaches is still considerably time-consuming and not suitable for applications like the interaction between Pt clusters and carbon surfaces.…”

Section: Introductionmentioning

confidence: 99%

Structural and electronic properties of the Pt_n–PAH complex (n = 1, 2) from density functional calculations

Mahmoodinia

Ebadi

Åstrand

et al. 2014

Phys. Chem. Chem. Phys.

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A detailed density functional study of the Pt atom and Pt dimer adsorption on a polyaromatic hydrocarbon (PAH) is presented. The preferred adsorption site for a Pt atom is confirmed to be the bridge site. Upon adsorption of a single Pt atom, however, it is found here that the electronic ground state changes from the triplet state (5d 9 6s 1 configuration) to the closed-shell singlet state (5d 10 6s 0 configuration), which consequently will affect the catalytic activity of Pt when single Pt atoms bind to a carbon surface. The preferred adsorption site for the Pt dimer in the upright configuration is the hollow site. In contrast to the adsorption of a single Pt atom, the formation of a Pt-C bond in the adsorption of a Pt dimer is not accompanied by a change in the spin state, so the most stable electronic state is still the triplet state. While the atomic charge on the Pt atoms and dimers (in parallel configuration) in the Pt n /PAH complex is positive, a negative charge is found on the upper Pt atom for the upright configuration, indicating that single layers of Pt atoms will have a different catalytic activity as compared to Pt clusters on a carbon surface. Comparing the Pt-C bond length and the charge transfer on different sites, the magnitude of the charge transfer decreases with bond elongation, indicating that the catalytic activity of the Pt atom and dimer can be changed by modifying its chemical surroundings. The adsorption energy for the Pt dimer on a PAH surface is larger than for two individual Pt atoms on the surface indicating that aggregation of Pt atoms on the PAH surface is favorable.

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“…This leads to a mass increase where m 0 is the rest mass and ν is the speed of the electron, which causes the effective Bohr radius to decrease for core s and p electrons (i.e. a radial contraction) [17]. This has two main effects on the electronic structure of a transition metal.…”

Section: Introductionmentioning

confidence: 99%

Sulfur K-edge XAS of WVO vs. MoVO bis(dithiolene) complexes: Contributions of relativistic effects to electronic structure and reactivity of tungsten enzymes

Tenderholt

Szilágyi

Holm

et al. 2007

Journal of Inorganic Biochemistry

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Molybdenum-or tungsten-containing enzymes catalyze oxygen atom transfer reactions involved in carbon, sulfur, or nitrogen metabolism. It has been observed that reduction potentials and oxygen atom transfer rates are different for W relative to Mo enzymes and the isostructural Mo/W complexes. Sulfur K-edge X-ray absorption spectroscopy (XAS) and density functional theory (DFT) calculations on [Mo V O(bdt) 2 ] − and [W V O(bdt) 2 ] − , where bdt = benzene-1,2-dithiolate(2−), have been used to determine that the energies of the half-filled redox-active orbital, and thus the reduction potentials and M=O bond strengths, are different for these complexes due to relativistic effects in the W sites.

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Relativistic effects in structural chemistry

Cited by 2,858 publications

References 38 publications

Density Functional Embedded Cluster Study of Cu₄, Ag₄ and Au₄ Species Interacting with Oxygen Vacancies on the MgO(001) Surface

Density Functional Embedded Cluster Study of Cu₄, Ag₄ and Au₄ Species Interacting with Oxygen Vacancies on the MgO(001) Surface

Structural and electronic properties of the Pt_n–PAH complex (n = 1, 2) from density functional calculations

Sulfur K-edge XAS of WVO vs. MoVO bis(dithiolene) complexes: Contributions of relativistic effects to electronic structure and reactivity of tungsten enzymes

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Relativistic effects in structural chemistry

Cited by 2,858 publications

References 38 publications

Density Functional Embedded Cluster Study of Cu4, Ag4 and Au4 Species Interacting with Oxygen Vacancies on the MgO(001) Surface

Density Functional Embedded Cluster Study of Cu4, Ag4 and Au4 Species Interacting with Oxygen Vacancies on the MgO(001) Surface

Structural and electronic properties of the Ptn–PAH complex (n = 1, 2) from density functional calculations

Sulfur K-edge XAS of WVO vs. MoVO bis(dithiolene) complexes: Contributions of relativistic effects to electronic structure and reactivity of tungsten enzymes

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Density Functional Embedded Cluster Study of Cu₄, Ag₄ and Au₄ Species Interacting with Oxygen Vacancies on the MgO(001) Surface

Density Functional Embedded Cluster Study of Cu₄, Ag₄ and Au₄ Species Interacting with Oxygen Vacancies on the MgO(001) Surface

Structural and electronic properties of the Pt_n–PAH complex (n = 1, 2) from density functional calculations