The Role of Radical Bridges in Polynuclear Single-Molecule Magnets

Employing radical bridges between anisotropic metal ions has been a viable route to achieve high-performance single-molecule magnets (SMMs). While the bridges have been mainly considered for their ability to promote exchange interactions, the crystal-field effect arising from them has not been taken into account explicitly. This lack of consideration may distort the understanding and limit the development of the entire family. To shed light on this aspect, herein we report a theoretical investigation of a series of N -radical-bridged diterbium complexes. It is found that while promoting strong exchange coupling between the terbium ions, the N -radical induces a crystal field that interferes destructively with that of the outer ligands, and thus reduces the overall SMM behavior. Based on the theoretical results, we conclude that the SMM behavior in this series could be further maximized if the crystal field of the outer ligands is designed to be collinear with that of the radical bridge. This conclusion can be generalized to all exchange-coupled SMMs.     

Influence of exciton-exciton interaction with spin paired charge carriers and exciton-lattice interaction on the surface properties of crystalline solids

Applying tight-binding approximation and spin pairing of like charge carriers in a pair of excitons created in a lattice, the possibility of forming a bound exciton-exciton state is studied. It is found that, provided there exists strong exciton-lattice interaction, such a bound state may be formed and its energy may lie within the valence band deforming the material into a crystalline solid with no energy gap. Lowering of the energy is calculated in naphthalene and anthracene crystals where some experimental results are known. The excess energy released after the formation of such bound state can be adequate, depending on the material, to desorb neutral atoms or eject of electrons from surfaces.     

Stability radii of positive linear Volterra-Stieltjes equations

We study stability radii of linear Volterra-Stieltjes equations under multi-perturbations and affine perturbations. A lower and upper bound for the complex stability radius with respect to multi-perturbations are given. Furthermore, in some special cases concerning the structure matrices, the complex stability radius can precisely be computed via the associated transfer functions. Then, the class of positive linear Volterra-Stieltjes equations is studied in detail. It is shown that for this class, complex, real and positive stability radius under multi-perturbations or multi-affine perturbations coincide and can be computed by simple formulae expressed in terms of the system matrices. As direct consequences of the obtained results, we get some results on robust stability of positive linear integro-differential equations and of positive linear functional differential equations. To the best of our knowledge, most of the results of this paper are new.     

Diffraction by a wedge at skew incidence: integral representations of Cauchy-Carleman for the electromagnetic fields

An electromagnetic diffraction problem in a wedge shaped region is reduced to a system of coupled functional difference equations by means of Sommerfeld integrals and Malyuzhinets theorem. By introducing an integral operator it is shown that the solutions of this system of functional equations can be defined in terms of integral representations whose kernels are solutions of a singular integral equation of Cauchy-Carleman type for which an explicit solution is given.     

Renormalization Effects in the Spectrum of a Coherently Driven Exciton–Biexciton System

Starting from the total Hamiltonian of an excited exciton–biexciton system, nonresonant renormalizations in the electronic spectrum of a coherently driven direct semiconductor are considered. Stringent group-theoretical inclusion of the particle spin in the Hamiltonian allows one to account for the dependence of different renormalization effects on polarizations of the incident laser fields. On the example of circularly polarized driving and probing pulses it is shown that the kind of observed renormalization is defined by the pump-and-probe polarization geometry. Thus, the exciton optical Stark effect must appear in the case of co-circular pump-and-probe, whereas a mixing of the polariton and biexciton spectra is possible only in the case of counter-circular pump-and-probe. The polariton--biexciton dispersion renormalization may manifest itself as synchronous splittings of the exciton--polariton and biexciton spectra under resonant pumping at a frequency of the polariton--biexciton transition, or in their shifts in opposite directions under near-resonant pumping. The mechanisms of both kinds of renormalization effects are analyzed, and the dependence of their characteristics on the pump parameters and microscopic parameters of the exciton–biexciton–photon system is established. An evaluation of the characteristics shows that the effect of polariton–biexciton dispersion renormalization dominates in the spectra of semiconductors with stable biexciton formation. Results of the theoretical study provide an adequate explanation of available experimental data.     

Kinetics of the hydrogen abstraction *CH3 + alkane --> CH4 + alkyl reaction class: an application of the reaction class transition state theory

Kinetics of the hydrogen abstraction reaction (*)CH(3) + CH(4) --> CH(4) + (*)CH(3) is studied by a direct dynamics method. Thermal rate constants in the temperature range of 300-2500 K are evaluated by the canonical variational transition state theory (CVT) incorporating corrections from tunneling using the multidimensional semiclassical small-curvature tunneling (SCT) method and from the hindered rotations. These results are used in conjunction with the Reaction Class Transition State Theory/Linear Energy Relationship (RC-TST/LER) to predict thermal rate constants of any reaction in the hydrogen abstraction class of (*)CH(3) + alkanes. Our analyses indicate that less than 40% systematic errors on the average exist in the predicted rate constants using the RC-TST/LER method while comparing to explicit rate calculations the differences are less than 100% or a factor of 2 on the average.     

Ultrasensitive single-cell proteomics workflow identifies >1000 protein groups per mammalian cell

We report on the combination of nanodroplet sample preparation, ultra-low-flow nanoLC, high-field asymmetric ion mobility spectrometry (FAIMS), and the latest-generation Orbitrap Eclipse Tribrid mass spectrometer for greatly improved single-cell proteome profiling. FAIMS effectively filtered out singly charged ions for more effective MS analysis of multiply charged peptides, resulting in an average of 1056 protein groups identified from single HeLa cells without MS1-level feature matching. This is 2.3 times more identifications than without FAIMS and a far greater level of proteome coverage for single mammalian cells than has been previously reported for a label-free study. Differential analysis of single microdissected motor neurons and interneurons from human spinal tissue indicated a similar level of proteome coverage, and the two subpopulations of cells were readily differentiated based on single-cell label-free quantification.

The combination of nanodroplet sample preparation, ultra-low-flow nanoLC, high-field asymmetric ion mobility spectrometry (FAIMS) and latest-generation mass spectrometry instrumentation provides dramatically improved single-cell proteome profiling.     

Prediction of brand stories spreading on social networks

Advances in Data Analysis and Classification - Online social network is a major media for many types of information communication. Although the primary purpose of social networks is to connect...