The development of hybrid organic-inorganic perovskite solar cells is one the most rapidly growing fields in photovoltaic community and on its way to challenge polycrystalline silicon thin film technologies. High power conversion efficiencies can be achieved by simple processing with low cost. However, due limited long-term stability environmental toxicity lead prototypic CH3NH3PbI3, there a need find alternative ABX3 constitutional combinations order promote commercialization. Goldschmidt...

Recently, several forms of unsupportedgold were shown to display a remarkable activity catalyze oxidation reactions. Experimental evidence points the crucial role residual silver present in very small concentrations these novel catalysts. We focus on catalytic properties nanoporous gold (np-Au) foams probed viaCO and oxygen adsorption/co-adsorption. results are analyzed using theoretical models represented by flat Au(111) kinked Au(321) slabs with Ag impurities. show that atoms incorporated...

We extend our recently reported embedding theory [J. Chem. Phys. 110, 7677 (1999)] to calculate not only improved descriptions of ground states, but now also localized excited states in a periodically infinite condensed phase. A local region the solid is represented by small cluster for which high quality quantum chemical calculations are performed. The interaction with extended phase taken into account an effective potential. This potential calculated periodic density functional (DFT) and...

Since Au turned out to be an active catalyst for CO oxidation at low temperatures, adsorption on various surfaces has been in the scope of numerous surface science studies. Interestingly, supported particles as well stepped and rough single-crystal exhibit very similar behavior. To elucidate origin these similarities, we have performed temperature-programmed desorption infrared absorption spectroscopy a whole range from nanoparticles grown HOPG Au(111) roughened by argon ion bombardment. In...

We present the first ab initio prediction of localized electronic excited states in a periodically infinite condensed phase, heretofore intractable goal. In particular, we examined local excitations within CO molecule adsorbed on Pd(111). The calculation allows configuration interaction treatment region, while its with extended phase is described via an embedding potential obtained from periodic density functional theory. Our work lays foundation microscopic understanding photochemistry and...

The formation of flexible self-assembled monolayers (SAMs) in which an external trigger modifies the geometry surface-anchored molecules is essential for development functional materials with tunable properties. In this work, it demonstrated that NO2 -functionalized N-heterocyclic carbene (NHCs), were anchored on Au (111) surface, change their orientation from tilted into flat-lying position following trigger-induced reduction nitro groups. DFT calculations identified energetic driving force...

The development of chemically addressable N-heterocyclic carbene (NHC) based self-assembled monolayers (SAMs) requires in-depth understanding the influence NHC's anchoring geometry on its chemical functionality. Herein, it is demonstrated that reactivity surface-anchored NO2-functionalized NHCs (NO2–NHCs) can be tuned by modifying distance between functional group and reactive surface, which governed deposition technique. Liquid NO2–NHCs Pt(111) induced a SAM in NO2-aryl groups were...

State resolved laser induced desorption of NO molecules from a NiO(100) surface is studied theoretically. A full potential energy for the excited state was constructed by means ab initio cluster calculations in addition to ground state. Multidimensional wave packet on these two surfaces allow detailed simulation experimental observables, such as velocity distributions and probabilities, basis.

In order to interpret the experimental results of state resolved UV-laser-induced desorption NO from NiO(100) (rotational and vibrational populations, velocity distributions desorbing molecules, etc.), we have performed ab initio complete active space self-consistent field (CASSCF) configuration interaction (CI) calculations for potential between surface in electronic ground those excited states which are involved process. The NiO(100)–NO distance tilt angle axis normal been varied. A...

An ultrafast photoinduced charge transfer event in condensed phase is simulated. The interaction with the field treated explicitly within a time-dependent framework. description of system its environment based on surrogate Hamiltonian method where infinite number degrees freedom approximated by finite set two-level modes for limited time. This well suited to events, since it not weak coupling between and environment. Moreover, influence external system-bath included naturally. generalized...

Palladium was vapor deposited on a thin FeO(111) film grown Pt(111) substrate. Scanning tunneling microscopy study has revealed that Pd wets the FeO substrate and at elevated temperatures forms extended Pd(111) monolayer islands in contrast to other oxide supports previously studied. For first time, we have imaged metal-oxide interface structure with atomic resolution explained results basis of ab initio calculations.

The adsorption of oxygen on kinked Au(321) slabs is investigated theoretically the basis density functional theory. On-surface, subsurface, and surface-oxide forms O are analyzed compared pure gold surfaces containing silver atoms. At low coverage (0.1 ML) subsurface species shown to be unstable both thermodynamically kinetically due a barrier for conversion stronger bound on-surface chemisorbed oxygen. presence Ag in near-surface region was increase binding strength as well O, but...

Nanoporous gold (np-Au) is a catalytically highly active material, prepared by selectively dealloying silver from gold–silver alloy. It can promote aerobic CO oxidation and range of other reactions. has been debated whether the remarkable catalytic properties np-Au are mainly due to its structural features or residual Ag remaining in material after decisive for activity, especially activation O2. Recent theoretical studies provided evidence that impurities facilitate adsorption dissociation...

We have performed a systematic density-functional study of the mercury chalcogenide compounds $\ensuremath{\beta}$-HgS, HgSe, and HgTe using an all-electron full-potential linear muffin-tin orbital method. find that, in zinc-blende structure, both HgSe are semimetals whereas $\ensuremath{\beta}$-HgS has small spin-orbit-induced band gap. Our calculated relativistic photoemission inverse spectra reproduce very well most recently measured spectra, as do also our theoretical optical spectra. In...

The power of silicon! unique [Si(S2O7)3]2− anion is the first example a tetravalent silicon atom coordinated by three chelating inorganic ligands (see graphic). It forms when SiCl4 reacts with oleum at elevated temperatures and has been crystallized as its sodium cesium salts. Detailed facts importance to specialist readers are published ”Supporting Information”. Such documents peer-reviewed, but not copy-edited or typeset. They made available submitted authors. Please note: publisher...

Electrospray ionization mass spectrometry (ESIMS) and subsequent tandem (MS/MS) analyses were used to study some important metathesis reactions with the first-generation ruthenium catalyst 1, focusing on complex intermediates in catalytic cycle. In situ cationization alkali cations (Li(+), Na(+), K(+), Cs(+)) using a microreactor coupled directly ESI ion source allowed spectrometric detection characterization of species present solution particularly catalytically active...

Nanoporous gold (np-Au) has recently emerged as a highly selective environmentally friendly catalyst for low-temperature applications. Despite the seeming simplicity of this material, which consists almost pure gold, its surface chemistry turns out to be more complex than anticipated. Interactions among chemisorbed O atoms generated and consumed during catalysis, trace amounts Ag impurities present in np-Au lead dynamics. In work, theoretical modeling by means ab initio molecular dynamics...

Sulfates united: The unique tetrasulfate S4O132− anion was observed in the structure of (NO2)2[S4O13] that forms reaction N2O5 with SO3. Theoretical investigations show is a stable member polysulfate series [SnO3n+1]2−, which investigated up to n=11. Detailed facts importance specialist readers are published as "Supporting Information". Such documents peer-reviewed, but not copy-edited or typeset. They made available submitted by authors. Please note: publisher responsible for content...

Abstract The reactions of group 14 tetrachlorides MCl 4 (M=Si, Ge, Sn) with oleum (65 % SO 3 ) at elevated temperatures lead to the unique complex ions [M(S 2 O 7 ] 2− , which show central M atoms in coordination three chelating S groups. mean distances MO within anions increase from 175.6(2)–177.5(2) pm (M=Si) 186.4(4)–187.7(4) (M=Ge) 201.9(2)–203.5(2) (M=Sn). These are reproduced well by DFT calculations. same calculations an increasing positive charge for atom row Si, Sn, can be...

Vereinigte Sulfate: Das einzigartige Tetrasulfat-Anion S3O132− konnte in der Struktur von (NO2)2[S4O13] beobachtet werden, die sich Reaktion N2O5 mit SO3 bildet. Theoretische Untersuchungen zeigen, dass das Anion ein stabiles Mitglied Polysulfatfamilie [SnO3n+1]2− ist, bis zu n=11 untersucht wurde. Detailed facts of importance to specialist readers are published as ”Supporting Information”. Such documents peer-reviewed, but not copy-edited or typeset. They made available submitted by the...

Introducing spectator molecules to the surface of supported noble metal nanoparticles is an innovative approach improve selectivity heterogeneous catalysts. Colloidal synthesis allows researchers select and nanoparticle size, as well subsequent particle loading on different supports under well-defined conditions. However, understanding interplay various effects that spectators can have catalytic properties surfaces still requires further development. In this work, dodecylamine (DDA) used...