Chemical bonding concepts like covalency, ionicity, Pauli repulsion, shared‐electron, or donor–acceptor are important tools to sort our vast knowledge in chemistry and predict new reactivity. Electronic structure analysis provides the basis for a detailed understanding of origins these concepts. Energy decomposition (EDA) is an established method molecules has recently been implemented application extended systems, that is, surfaces solids, where it termed periodic EDA (pEDA). The...

By using computational chemistry it has been shown that the adsorption of ether molecules on Si(001) under ultrahigh vacuum conditions can be understood with classical concepts organic chemistry. Detailed analysis two-step reaction mechanism-1) formation a dative bond between oxygen atom and Lewis acidic surface 2) nucleophilic attack nearby basic atom-shows mirrors acid-catalyzed cleavage in solution. The O-Si is strongest its kind, reactivity step 2 defies Bell-Evans-Polanyi principle....

Abstract Intermediate states to covalent attachment of molecules on surfaces, so called precursors, are usually considered be physisorbed and mobile. We show that this view should reconsidered provide evidence for a chemisorbed precursor ethylene Si(001). The character the molecule‐surface bond as π complex is determined quantified using our recently developed method energy charge analysis in extended systems. In contrast previous assumptions, thus immobile, which underlined by computation...

Abstract Am 11. Februar veranstalteten Chemistry Europe und Angewandte Chemie in den Wiley‐VCH‐Büros Berlin Weinheim das sechste Netzwerkevent anlässlich des IUPAC Global Women’s Breakfast. Die beiden Büros waren einander online zugeschaltet. Über 60 Teilnehmende von Universitäten, aus der Industrie, Wissenschaftskommunikation Redaktionen Chemiezeitschriften tauschten sich darüber aus, wie Karriere Akademia Elternschaft vereinbaren lassen. Drei Vorträge zu persönlichen Erfahrungen als Eltern...

Abstract The adsorption characteristics of a promising system for hybrid organic–inorganic interfaces, cyclooctyne on Si(001), is analyzed using density functional theory. chemisorbed ′on‐top′ configuration, where cycloadduct formed between the ring triple bond and surface dimer, shown to be most stable. Less stable are ′bridge′ ′sublayer′ modes featuring two molecule‐surface bonds ′pedestal′ mode with four bonds. Investigations our recently proposed periodic energy decomposition analysis...

Abstract Differences in adsorption and reaction energetics for ethylene on Si(001) are reported with respect to distorted dangling‐bond configurations induced by hydrogen precoverage, as obtained DFT calculations. This can help understand the influence of surface defects precoverage reactivity organic molecules semiconductor surfaces general. The results show that dimers fully enclosed hydrogen‐covered atoms is essentially unchanged compared clean surface. confirmed scanning tunneling...

Surprising adsorption dynamics in terms of an either direct or pseudodirect pathway contrast to common precursor-mediated surface reactions is shown for the title system by theoretical investigations. We present a computational protocol description this complex that transferable other large molecules. The size prohibits use established accurate methods, and approximations have be made validated. Our approach combines potential energy scans, reaction path determination statistical...

Pressure shows a strong influence on aerosol yields from the gas phase ozonolysis of terpenes and other cyclic alkenes.

Using density functional theory (DFT) methods, we analyze the adsorption of acetylene and ethylene on Si(001) surface in an unusual bond insertion mode. The takes place at a saturated tetravalent silicon atom insight gained can thus be transferred to other compounds molecular chemistry. Molecular orbital analysis reveals that distorted symmetry-reduced coordination atoms involved due reconstruction raises electrophilicity and, additionally, makes certain σ orbitals more accessible. affinity...

Silver complexes involving vinyltrifluoroborate, (IPr)Ag(CH 2 =CHBF 3 ) ( 4 ), [(IPr) Ag][CH ] 5 (SIPr)Ag(CH 6 and (IPr*)Ag(CH 7 have been synthesized by using (NHC)AgNO [NHC = IPr 1 SIPr IPr* )] K(CH in a metathesis process. NMR spectroscopic details of – X‐ray crystal structures compounds as well that precursor (IPr)AgNO are reported. Compounds more stable solution compared to (which forms indicating supporting ligand effect the stability monomeric (NHC)Ag(CH ). Calculated metal–ligand...

The chemistry of organic adsorbates on surfaces is often discussed in terms Pauli repulsion as limiting factor regarding the packing molecules. Here we show that attractive part van der Waals potential can be similarly decisive. For semiconductor surface Si(001), an already covalently bonded molecule cyclooctyne steers a second incoming via dispersion interactions onto neighbouring adsorption site. This helps understanding nonstatistical pattern formation for this surface–adsorbate system...

Abstract Invited for the cover of this issue is group Ralf Tonner at University Marburg. The image depicts anchoring cyclooctyne to a Si(001) surface. Read full text article 10.1002/chem.201605952 .

To better support researchers and contribute constructively to international scientific discourse, Angewandte Chemie has launched two opinion‐based article categories with the of German Chemical Society (GDCh) journal's governing bodies. Scientific Perspectives outline best practice in chemical sciences while Viewpoint Articles address culture community.

Abstract Wir zeigen mit quantenchemischen Methoden, dass sich die Adsorption von Ether‐Molekülen auf Si(001) im Ultrahochvakuum durch klassische Konzepte der organischen Molekülchemie verstehen lässt. Wie unsere detaillierte Analyse zeigt, spiegelt zweistufige Mechanismus – 1) Ausbildung einer dativen Bindung zwischen dem Sauerstoffatom am Ether und einem Lewis‐sauren Oberflächenatom, 2) nukleophiler Angriff eines nahegelegenen Lewis‐basischen Oberflächenatoms säurekatalysierte Etherspaltung...

Abstract The front cover artwork is provided by Aaron Beller (Faculty of Arts, Philipps‐Universität Marburg) in collaboration with the authors. image shows how firm grip a dative bond, indicated black arrow, prevents weakly adsorbed ethylene molecule from moving on Si(001) surface. Read full text article at 10.1002/cphc.201601129 .

Computational modeling of organic interface formation on semiconductors poses a challenge to density functional theory-based description due structural and chemical complexity. A hierarchical approach is presented, where parts the are successively removed in order increase computational efficiency while maintaining necessary accuracy. First, benchmark performed probe validity this for three model reactions five dispersion corrected functionals. Reaction energies generally well reproduced by...

Abstract Computational modeling of organic interface formation on semiconductors poses a challenge to density functional theory‐based description due structural and chemical complexity. A hierarchical approach is presented, where parts the are successively removed in order increase computational efficiency while maintaining necessary accuracy. First, benchmark performed probe validity this for three model reactions five dispersion corrected functionals. Reaction energies generally well...

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