Kinetic oscillations in the rate of CO oxidation on Pd(110)

The oxidation of carbon monoxide on a Pd(110) single crystal plane has been studied using work function changes (Δφ) and mass spectrometric measurements. The rate of reaction showed oscillatory behaviour for oxygen pressures greater than 10⁻³ Torr. The existence region for oscillations was determined for pressures ranging from 10⁻³ to 1.0 Torr and depended on the pressures of oxygen and carbon monoxide and the sample temperature (P_co, PO₂ T). Transitions from regular oscillation to chaos via period doubling have been observed in certain areas of the existence region. A comparison between Pd(110) and platinum single crystal surfaces that exhibit oscillations showed that similar but not identical oscillatory behaviour and existence regions exist in each case. Our results indicate that oscillations can occur on other metal single crystal surface that are less likely than platinum to reconstruct under reaction conditions. The extension of oscillations from UHV conditions to the 1.0 Torr pressure region indicates that the mechanism responsible for isothermal oscillations is basically independent of the reactant pressure up to several Torr.     

Highly selective addition of cyclosilanes to alkynes enabling new conjugated materials

Main group organometallic compounds can exhibit unusual optical properties arising from hybrid σ,π-conjugation. While linear silanes are extensively studied, the shortage of methods for the controlled synthesis of well-defined cyclic materials has precluded the study of cyclic conjugation. Herein we report that Ru-catalyzed addition of cyclosilanes to aryl acetylenes (hydrosilylation) proceeds with high chemoselectivity, regioselectivity, and diastereoselectivity, affording complex organosilanes that absorb visible light. We further show that the hydrosilylation products are useful building blocks towards novel conjugated polymers.

Hybrid σ,π-conjugated cyclosilanes were synthesized via highly selective hydrosilylation and have shown great potentials as building blocks to construct novel conjugated polymers with control of tacticity.     

In Situ Synthesis and Applications for Polyinterhalides Based on BrCl

The use of neat BrCl in organic and inorganic chemistry is limited due to its gaseous aggregate state and especially its decomposition into Cl₂ and Br₂. The stabilization of BrCl in form of reactive ionic liquids via a novel in situ synthesis route shifts this equilibrium drastically to the BrCl side, which leads to safer and easier-to-handle interhalogenation reagents. Furthermore, the crystalline derivatives of the hitherto unknown [Cl(BrCl)₂]⁻ and [Cl(BrCl)₄]⁻ anions were synthesized and characterized by single-crystal X-ray diffraction (XRD), Raman and IR spectroscopy, as well as quantum chemical calculations.     

2D Oligosilyl Metal–Organic Frameworks as Multi-state Switchable Materials

We report the synthesis of a set of 2D metal–organic frameworks (MOFs) constructed with organosilicon-based linkers. These oligosilyl MOFs feature linear Si_nMe_2n(C₆H₄CO₂H)₂ ligands (lin-Si_n, n=2, 4) connected by Cu paddlewheels. The stacking arrangement of the 2D sheets is dictated by van der Waals interactions and is tunable by solvent exchange, leading to reversible structural transformations between many crystalline and amorphous phases.     

Jahn–Teller Distortion Versus Spin–Orbit Splitting: Symmetry of Small Heavy-Metal Atom Clusters

Metal clusters often show slight deviations from high molecular point group symmetry. The reason for this is a Jahn–Teller distortion because of partial occupation of orbitals that are degenerate in the highly symmetric case. For heavy elements spin–orbit coupling, which usually is not regarded in quantum chemical treatments of clusters, becomes non-negligible. This leads to splitting of degenerate orbitals, so that the reason for distortion is no longer given. In a rigorous study of neutral, cationic and anionic 4–6 atomic clusters of W, Re, Tl and Pb it is demonstrated that in some cases regarding spin–orbit coupling indeed yields a highly symmetric global minimum structure, whereas neglecting this effect leads to distorted structures of lower symmetry.     

A review on consistency and robustness properties of support vector machines for heavy-tailed distributions

Support vector machines (SVMs) belong to the class of modern statistical machine learning techniques and can be described as M-estimators with a Hilbert norm regularization term for functions. SVMs are consistent and robust for classification and regression purposes if based on a Lipschitz continuous loss and a bounded continuous kernel with a dense reproducing kernel Hilbert space. For regression, one of the conditions used is that the output variable Y has a finite first absolute moment. This assumption, however, excludes heavy-tailed distributions. Recently, the applicability of SVMs was enlarged to these distributions by considering shifted loss functions. In this review paper, we briefly describe the approach of SVMs based on shifted loss functions and list some properties of such SVMs. Then, we prove that SVMs based on a bounded continuous kernel and on a convex and Lipschitz continuous, but not necessarily differentiable, shifted loss function have a bounded Bouligand influence function for all distributions, even for heavy-tailed distributions including extreme value distributions and Cauchy distributions. SVMs are thus robust in this sense. Our result covers the important loss functions ${\epsilon}$ -insensitive for regression and pinball for quantile regression, which were not covered by earlier results on the influence function. We demonstrate the usefulness of SVMs even for heavy-tailed distributions by applying SVMs to a simulated data set with Cauchy errors and to a data set of large fire insurance claims of Copenhagen Re.     

Dynamical consequences of symmetry breaking in benzene and difluorobenzene

The systems benzene/benzene-d(1) and o-/m-/p-difluorobenzene were studied in the dense gas phase with ultrafast transient absorption spectroscopy to investigate the effect of symmetry reduction through monodeuteration and constitutional isomerism on the timescales of intramolecular vibrational energy redistribution (IVR). In both systems IVR proceeds faster in the molecules of lower symmetry. In addition the dynamics were simulated in vibrational quantum number space using a simple model based on scaling state-to-state interactions by coupling order and the energy gap law. These simulations (semi-) quantitatively reproduce the experimental data for benzene and benzene-d(1) without incorporating further molecular symmetry restrictions. The relative impact of molecular symmetry and vibrational state space structure on IVR is discussed.