Francesc Illas

Support nanostructure boosts oxygen transfer to catalytically active platinum nanoparticles

Interactions of metal particles with oxide supports can radically enhance the performance of supported catalysts. At the microscopic level, the details of such metal-oxide interactions usually remain obscure. This study identifies two types of oxidative metal-oxide interaction on well-defined models of technologically important Pt-ceria catalysts: (1) electron transfer from the Pt nanoparticle to the support, and (2) oxygen transfer from ceria to Pt. The electron transfer is favourable on ceria supports, irrespective of their morphology. Remarkably, the oxygen transfer is shown to require the presence of nanostructured ceria in close contact with Pt and, thus, is inherently a nanoscale effect. Our findings enable us to detail the formation mechanism of the catalytically indispensable Pt-O species on ceria and to elucidate the extraordinary structure-activity dependence of ceria-based catalysts in general.

Establishing the Accuracy of Broadly Used Density Functionals in Describing Bulk Properties of Transition Metals.

The performance of various commonly used density functionals is established by comparing calculated values of atomic structure data, cohesive energies, and bulk moduli of all transition metals to available experimental data. The functionals explored are the Ceperley-Alder (CA), Vosko-Wilk-Nussair (VWN) implementation of the Local Density Approximation (LDA); the Perdew-Wang (PW91) and Perdew-Burke-Ernzerhof (PBE) forms of the Generalized Gradient Approximation (GGA), and the RPBE and PBEsol modifications of PBE, aimed at better describing adsorption energies and bulk solid lattice properties, respectively. The present systematic study shows that PW91 and PBE consistently provide the smallest differences between the calculated and experimental values. Additional calculations of the (111) surface energy of several face centered cubic (fcc) transition metals reveal that LDA produces the most accurate results, while all other functionals significantly underestimate the experimental values. RPBE severely underestimates surface energy, which may be the origin for the reduced surface chemical activity and the better performance of RPBE describing adsorption energies.

Accounting for van der Waals interactions between adsorbates and surfaces in density functional theory based calculations: selected examples

This article reviews the different density functional theory (DFT) methods available in the literature for dealing with dispersion interactions and recent applications of DFT approaches including van der Waals corrections in the study of the interaction of atoms and molecules with several different surfaces. Focus is given to the interaction of atoms and molecules with metal, metal oxide and graphite surfaces or more complex systems. It will be shown that DFT approaches including van der Waals corrections present significant advances over standard exchange–correlation functionals for treating systems dominated by weak interactions.

Theoretical assessment of graphene-metal contacts

Graphene-metal contacts have emerged as systems of paramount importance in the synthesis of high-quality and large-size patches of graphene and as vital components of nanotechnological devices. Herein, we study the accuracy of several density functional theory methods using van der Waals functionals or dispersive forces corrections when describing the attachment of graphene on Ni(111). Two different experimentally observed chemisorption states, top-fcc and bridge-top, were put under examination, together with the hcp-fcc physisorption state. Calculated geometric, energetic, and electronic properties were compared to experimental data. From the calculations, one finds that (i) predictions made by different methodologies differ significantly and (ii) optB86b-vdW functional and Grimme dispersion correction seem to provide the best balanced description of stability of physisorption and chemisorption states, the attachment strength of the latter on Ni(111) surface, the graphene-Ni(111) separation, and the bandstructure of chemisorbed graphene. The collation suggests that accurate and affordable theoretical studies on technologies based on graphene-metal contacts are already at hand.

Magnetic Coupling in Transition-Metal Binuclear Complexes by Spin-Flip Time-Dependent Density Functional Theory.

Spin-flip time-dependent density functional theory (SF-TDDFT) has been applied to predict magnetic coupling constants for a database of 12 spin-1/2 homobinuclear transition-metal complexes previously studied by Phillips and Peralta employing spin-projected broken-symmetry density functional theory (Phillips, J. J.; Peralta, J. E. J. Chem. Phys.2011, 134, 034108). Several global hybrid density functionals with a range of percentages of Hartree-Fock exchange from 20% to 100% have been employed within the collinear-spin formalism, and we find that both the high-spin reference state and low-spin state produced by SF-TDDFT are generally well adapted to spin symmetry. The magnetic coupling constants are calculated from singlet-triplet energy differences and compared to values arising from the popular broken-symmetry approach. On average, for the density functionals that provide the best comparison with experiment, the SF-TDDFT approach performs as well as or better than the spin-projected broken-symmetry strategy. The constrained density functional approach also performs quite well. The SF-TDDFT magnetic coupling constants show a much larger dependence on the percentage of Hartree-Fock exchange than on the other details of the exchange functionals or the nature of the correlation functionals. In general, SF-TDDFT calculations not only avoid the ambiguities associated with the broken-symmetry approach, but also show a considerably reduced systematic deviation with respect to experiment and a larger antiferromagnetic character. We recommend MPW1K as a well-validated hybrid density functional to calculate magnetic couplings with SF-TDDFT.

Density functional theory model study of size and structure effects on water dissociation by platinum nanoparticles

Size and structure effects on the homolytic water dissociation reaction mediated by Pt nanoparticles have been investigated through density functional theory calculations carried out on a series of cubooctahedral Pt(n) nanoparticles of increasing sizes (n = 13, 19, 38, 55, 79, and 140). Water adsorption energy is not significantly influenced by the nanoparticle size. However, activation energy barrier strongly depends on the particle size. In general, the activation energy barrier increases with nanoparticles size, varying from 0.30 eV for Pt(19) to 0.70 eV for Pt(140). For the largest particle the calculated barrier is very close to that predicted for water dissociation on Pt(111) (0.78 eV) even though the reaction mediated by the Pt nanoparticles involves adsorption sites not present on the extended surface.

Toward the design of ferromagnetic molecular complexes: magnetostructural correlations in ferromagnetic triply bridged dinuclear Cu(II) compounds containing carboxylato and hydroxo bridges.

In the present work we present a comprehensive study of the magneto-structural correlations of a series of ferromagnetic triply heterobridged Cu(II) dinuclear compounds containing [Cu(2)(mu-O(2)CR)(mu-OH)(mu-X)(L)(2)](2+) ions (where X = OH(2), Cl(-), OMe(-) and L = bpy, phen, dpyam) which have the particularity of being all ferromagnetic. The present theoretical study, based on hybrid density functional theory (DFT) calculations, leads to strong conclusions about the role of the pentacoordination geometry of the Cu(II) ions (square base pyramidal (SP) or trigonal bipyramidal (TBP) coordination) and the nature of the third bridging ligand in determining the final value of the magnetic coupling constants in this series of compounds. These investigations point toward the existence of a maximum value for the ferromagnetic interaction and may offer some useful information to synthetic chemists aiming at obtaining new compounds with enhanced ferromagnetism.

Role of step sites on water dissociation on stoichiometric ceria surfaces

The adsorption and dissociation of water on CeO2(111), CeO2(221), CeO2(331), and CeO2(110) has been studied by means of periodic density functional theory using slab models. The presence of step sites moderately affects the adsorption energy of the water molecule but in some cases as in CeO2(331) is able to change the sign of the energy reaction from endo- to exothermic which has important consequences for the catalytic activity of this surface. Finally, no stable molecular state has been found for water on CeO2(110) where the reaction products lead to a very stable hydroxylated surface which will rapidly become inactive.

New series of triply bridged dinuclear Cu(II) compounds: synthesis, crystal structure, magnetic properties, and theoretical study.

Five new triply bridged dinuclear Cu(II) compounds have been synthesized, and their magnetic properties have been measured and characterized. The magnetic coupling constants (J) of these compounds plus a previously structurally characterized compound of the same type have been derived by appropriate fitting of the experimentally measured molar susceptibility variation with the temperature. Two of the compounds are ferromagnetically coupled, and three are antiferromagnetically coupled with J values in the [+150, -40] cm(-1) range. The validity of the structural aggregate Addisons parameter as a qualitative magneto-structural correlation is confirmed. The origin of the magnetic interactions and the magnitude of the magnetic coupling have been analyzed by means of density functional theory-based calculations using a variety of state of the art exchange-correlation potentials. It is shown that the long-range separated LC-ωPBE provides the overall best agreement with experiment for this family as well as for a set of previously reported hetero triply bridged dinuclear Cu(II) compounds, especially for ferromagnetic systems.

Origin of optical excitations in fluorine-doped titania from response function theory: Relevance to photocatalysis

We investigate the effect of fluorine doping on the optical spectra of stoichiometric and reduced TiO2 anatase, brookite, and rutile using density functional methods. The present approach is able to reproduce the main features of experiments and high-level quasiparticle calculations for undoped titania but at a much lower computational cost, thus allowing the study of doped titania, which requires large supercells. Whereas the simulated spectra of F-substituted brookite and rutile do not show any significant new feature, a relatively intense new band near the visible region is predicted for F-substituted anatase. This allows one to suggest assigning the spectral features near the visible region, observed on multiphase F-doped titania samples, to the presence of anatase. The physical origin of the new absorption band in F-doped anatase is unambiguously attributed to the presence of Ti(3+) centers.