QuantumATK: an integrated platform of electronic and atomic-scale modelling tools.

QuantumATK is an integrated set of atomic-scale modelling tools developed since 2003 by professional software engineers in collaboration with academic researchers. While different aspects and individual modules of the platform have been previously presented, the purpose of this paper is to give a general overview of the platform. The QuantumATK simulation engines enable electronic-structure calculations using density functional theory or tight-binding model Hamiltonians, and also offers bonded or reactive empirical force fields in many different parametrizations. Density functional theory is implemented using either a plane-wave basis or expansion of electronic states in a linear combination of atomic orbitals. The platform includes a long list of advanced modules, including Green's-function methods for electron transport simulations and surface calculations, first-principles electron-phonon and electron-photon couplings, simulation of atomic-scale heat transport, ion dynamics, spintronics, optical properties of materials, static polarization, and more. Seamless integration of the different simulation engines into a common platform allows for easy combination of different simulation methods into complex workflows. Besides giving a general overview and presenting a number of implementation details not previously published, we also present four different application examples. These are calculations of the phonon-limited mobility of Cu, Ag and Au, electron transport in a gated 2D device, multi-model simulation of lithium ion drift through a battery cathode in an external electric field, and electronic-structure calculations of the composition-dependent band gap of SiGe alloys.

Unravelling Site-Specific Photo-Reactions of Ethanol on Rutile TiO2(110).

Finding the active sites of catalysts and photo-catalysts is crucial for an improved fundamental understanding and the development of efficient catalytic systems. Here we have studied the photo-activated dehydrogenation of ethanol on reduced and oxidized rutile TiO2(110) in ultrahigh vacuum conditions. Utilizing scanning tunnelling microscopy, various spectroscopic techniques and theoretical calculations we found that the photo-reaction proceeds most efficiently when the reactants are adsorbed on regular Ti surface sites, whereas species that are strongly adsorbed at surface defects such as O vacancies and step edges show little reaction under reducing conditions. We propose that regular Ti surface sites are the most active sites in photo-reactions on TiO2.

Effect of Sb Segregation on Conductance and Catalytic Activity at Pt/Sb-Doped SnO2 Interface: A Synergetic Computational and Experimental Study.

Antimony-doped tin dioxide (ATO) is considered a promising support material for Pt-based fuel cell cathodes, displaying enhanced stability over carbon-based supports. In this work, the effect of Sb segregation on the conductance and catalytic activity at Pt/ATO interface was investigated through a combined computational and experimental study. It was found that Sb-dopant atoms prefer to segregate toward the ATO/Pt interface. The deposited Pt catalysts, interestingly, not only promote Sb segregation, but also suppress the occurrence of Sb(3+) species, a charge carrier neutralizer at the interface. The conductivity of ATO was found to increase, to a magnitude close to that of activated carbon, with an increment of Sb concentration before reaching a saturation point around 10%, and then decrease, indicating that Sb enrichment at the ATO surface may not always favor an increment of the electric current. In addition, the calculation results show that the presence of Sb dopants in ATO has little effect on the catalytic activity of deposited three-layer Pt toward the oxygen reduction reaction, although subsequent alloying of Pt and Sb could lower the corresponding catalytic activity. These findings help to support future applications of ATO/Pt-based materials as possible cathodes for proton exchange membrane fuel cell applications with enhanced durability under practical applications.

A density functional theory study of atomic steps on stoichiometric rutile TiO2(110).

We present a detailed theoretical study of the energetics of stoichiometric steps on the (110) surface of rutile TiO2. Step structures running along the <001>, <111>, and <110> directions including bulk-terminations and possible reconstructions have been considered. A robust method for extracting surface and step energies of vicinal surfaces, where the surface energies converge slowly with respect to slab thickness, is outlined and used. Based on the calculated step energies a 2D Wulff-construction is presented from which it can be concluded that in equilibrium only oxygen terminated steps running along the <001> directions and reconstructed steps along the <111> directions should be present. Finally it is found that under conditions of stoichiometry the reconstructed <111> steps should be more than twice as abundant as oxygen terminated <001> steps.

Ethanol Diffusion on Rutile TiO2(110) Mediated by H Adatoms.

We have studied the diffusion of ethanol on rutile TiO2(110)-(1 × 1) by high-resolution scanning tunneling microscopy (STM) measurements and density functional theory (DFT) calculations. Time-lapsed STM images recorded at ∼200 K revealed the diffusion of ethanol molecules both parallel and perpendicular to the rows of surface Ti atoms. The diffusion of ethanol molecules perpendicular to the rows of surface Ti atoms was found to be mediated by H adatoms in the rows of bridge-bonded O (Obr) atoms similarly to previous results obtained for water monomers. In contrast, the diffusion of H adatoms across the Ti rows, mediated by ethanol molecules, was observed only very rarely and exclusively on fully hydrogenated TiO2(110) surfaces. Possible reasons why the diffusion of H adatoms across the Ti rows mediated by ethanol molecules occurs less frequently than the cross-row diffusion of ethanol molecules mediated by H adatoms are discussed.

Adsorption properties versus oxidation states of rutile TiO2(110).

Using density functional theory we have studied the adsorption properties of different atoms and molecules deposited on a stoichiometric, reduced, and oxidized rutile TiO(2)(110) surface. Depending on the oxidation state of the surface, electrons can flow from or to the substrate and, therefore, negatively or positively charged species are expected. In particular, we have found that a charge transfer process from or to the surface always occurs for highly electronegative or highly electropositive species, respectively. For atoms or molecules with intermediate electron affinity, the direction of the charge flow depends on the oxidation state of the rutile surface and on the adsorption site. Generally, the charging effect leads to more stable complexes. However, the increase in the binding energy of the adsorbates is highly dependent on the electronic states of the surface prior to the adsorption event. In this work we have analyzed in details these mechanisms and we have also established a direct correlation between the enhanced binding energy of the adsorbates and the induced gap states.

Direct measurement of the attractive interaction forces on F0 color centers on MgO(001) by dynamic force microscopy.

Defect sites on oxide surfaces play a dominant role in surface chemistry. The direct atomistic study of these sites is important but very difficult. We have mimicked the adsorbate-defect interaction by a dynamic force microscope tip measuring the interaction with a color center (F(0)) on the MgO(001) surface. The experimental findings, complemented by density functional theory calculations, show a highly attractive adsorbate-defect interaction and a charge transfer at a critical distance.

Stabilizing monomeric iron species in a porous silica/Mo(112) film.

The stabilization of single Fe atoms in the nanopores of an ultrathin silica film grown on Mo(112) is demonstrated with scanning tunneling microscopy (STM) and density functional theory (DFT). The Fe atoms are able to penetrate the openings in the oxide surface and adsorb in two different binding configurations at the metal-oxide interface. In the energetically preferred site, the Fe stays monomeric even at temperatures above 300 K. In the second configuration that is adopted in 10% of the cases, surface atoms can be attached to the subsurface species, resulting in the formation of Fe surface clusters. The interfacial Fe atoms preserve their magnetic moment, as shown by a distinct Kondo-like response in STM conductance spectra and DFT calculations.

Mechanism of charging of Au atoms and nanoclusters on Li doped SiO2/Mo(112) films.

We present the results of supercell DFT calculations on the adsorption properties of Au atoms and small clusters (Au(n), n < or = 5) on a SiO(2)/Mo(112) thin film and on the same system modified by doping with Li atoms. The adsorbed Li atoms penetrate into the pores of the silica film and become stabilized at the interface where they donate one electron to the Mo metal. As a consequence, the work function of the Li-doped SiO(2)/Mo(112) film is reduced and results in modified adsorption properties. In fact, while on the undoped SiO(2)/Mo(112) film Au interacts only very weakly, on the Li-doped surface Au atoms and clusters bind with significant bond strengths. The calculations show that this is due to the occurrence of an electron transfer from the SiO(2)/Mo(112) interface to the adsorbed gold. The occurrence of the charge transfer is related to the work function of the support but also to the possibility for the silica film to undergo a strong polaronic distortion.

Tailoring the interaction strength between gold particles and silica thin films via work function control.

The possibility to modify the adsorption properties of a porous silica/Mo(112) film by controlling its work function has been studied by a combined STM and density-functional theory approach. While the original film is inert towards metal adsorption, Au atoms and clusters can be stabilized on the surface after Li doping. The Li atoms penetrate the topmost silica layer and bind as Li+ cations at the metal-oxide interface, thereby reducing the oxide work function. This induces a charge transfer into Au adatoms, which in turn enables strong Au-silica interaction mediated by a polaronic distortion of the oxide lattice.

Enhanced magnetic moments of Fe clusters supported on MgO/Fe(001) ultrathin films.

We report on the unusual behavior of Fe(n) clusters (n < or = 6) supported on ultrathin oxide films. When the film is grown on a Mo(001) support, the cluster magnetic moments exhibit a similar quenching as on the bare MgO(001) surface while on MgO/Fe(001) films the magnetization is enhanced due to a charge transfer from the Fe clusters to the MgO/Fe(001) interface. These results obtained using a spin-polarized density functional approach show the potential of using ultrathin films to tune the properties of supported magnetic particles.

Modifying the adsorption characteristic of inert silica films by inserting anchoring sites.

The adsorption properties of thin silica films on Mo(112) have been tailored by embedding single Pd atoms into the nanopores of the oxide material. The embedded Pd is able to anchor metal adatoms that would not bind to the inert silica surface otherwise. Several adsorption structures, e.g., Pd-Pd, Ag-Pd, and Au-Pd complexes, have been prepared in this way and analyzed with the STM and density functional theory. The binding strength of the different adatoms to the surface is determined by the number of electrons in their frontier orbitals, which introduce a repulsive interaction with the oxide electronic states and weaken the covalent bond to the Pd anchor.

Tuning the work function of ultrathin oxide films on metals by adsorption of alkali atoms.

We report a theoretical investigation of the adsorption of alkali metal atoms deposited on ultrathin oxide films. The properties of Li, Na, and K atoms adsorbed on SiO(2)/Mo(112) and of K on MgO / Ag(100) and TiO(2)/Pt(111) have been analyzed with particular attention to the induced changes in the work function of the system, Phi. On the nonreducible SiO(2) and MgO oxide films there is a net transfer of the outer ns electron of the alkali atom to the metal substrate conduction band; the resulting surface dipole substantially lowers Phi. The change in Phi depends (a) on the adsorption site (above the oxide film or at the interface) and (b) on the alkali metal coverage. Deposition of K on reducible TiO(2) oxide films results in adsorbed K(+) ions and in the formation of Ti(3+) ions. No charge transfer to the metal substrate is observed but also in this case the surface dipole resulting from the K-TiO(2) charge transfer has the effect to considerably reduce the work function of the system.

Observable consequences of formation of Au anions from deposition of Au atoms on ultrathin oxide films.

Charging of metal atoms or clusters on oxide surfaces has important consequences on their chemical and physical properties. Recently it is has been shown that negatively charged gold atoms and clusters form spontaneously from neutral Au atoms deposited on ultrathin MgO films. The formation of anions on the surface remains difficult to prove experimentally. Also theoretically, the discrimination between neutral and charged adsorbed species is not straightforward. In this paper we perform an accurate analysis of the observable consequences of the formation of Au anions on an oxide surface. To this end we consider the following properties: spin distribution, density of states, Bader charges, substrate relaxation, simulated scanning tunneling microscopy images, work function changes, CO vibrational frequency, electric field effects, and core level shifts. Most of these properties are accessible experimentally, at least in principle. Taken individually, these properties do not necessarily provide conclusive evidence about the charged nature of the adsorbate. Taken together, they offer a complete and unambiguous characterization of the formation of Au anions.

Nature of point defects on SiO2/Mo(112) thin films and their interaction with Au atoms.

We have studied by means of periodic DFT calculations the structure and properties of point defects at the surface of ultrathin silica films epitaxially grown on Mo(112) and their interaction with adsorbed Au atoms. For comparison, the same defects have been generated on an unsupported silica film with the same structure. Four defects have been considered: nonbridging oxygen (NBO, [triple bond]Si-O(*)), Si dangling bond (E' center, [triple bond]Si(*)), oxygen vacancy (V(O), [triple bond]Si-Si[triple bond]), and peroxo group ([triple bond]Si-O-O-Si[triple bond]), but only the NBO and the V(O) centers are likely to form on the SiO(2)/Mo(112) films under normal experimental conditions. The [triple bond]Si-O(*) center captures one electron from Mo forming a silanolate group, [triple bond]Si-O(-), sign of a direct interaction with the metal substrate. Apart from the peroxo group, which is unreactive, the other defects bind strongly the Au atom forming stable surface complexes, but their behavior may differ from that of the same centers generated on an unsupported silica film. This is true in particular for the two most likely defects considered, the nonbridging oxygen, [triple bond]Si-O(*), and the oxygen vacancy, [triple bond]Si-Si[triple bond].