Fresnel laws at curved dielectric interfaces of microresonators

We discuss curvature corrections to Fresnel's laws for the reflection and transmission of light at a non-planar refractive-index boundary. The reflection coefficients are obtained from the resonances of a dielectric disk within a sequential-reflection model. The Goos-H\"anchen effect for curved light fronts at a planar interface can be adapted to provide a qualitative and quantitative extension of the ray model which explains the observed deviations from Fresnel's laws.Comment: submitted to Phys. Rev.

Prediction of persistent post-surgery pain by preoperative cold pain sensitivity : biomarker development with machine-learning-derived analysis

Background. To prevent persistent post-surgery pain, early identification of patients at high risk is a clinical need. Supervised machine-learning techniques were used to test how accurately the patients' performance in a preoperatively performed tonic cold pain test could predict persistent post-surgery pain. Methods. We analysed 763 patients from a cohort of 900 women who were treated for breast cancer, of whom 61 patients had developed signs of persistent pain during three yr of follow-up. Preoperatively, all patients underwent a cold pain test (immersion of the hand into a water bath at 2-4 degrees C). The patients rated the pain intensity using a numerical ratings scale (NRS) from 0 to 10. Supervised machine-learning techniques were used to construct a classifier that could predict patients at risk of persistent pain. Results. Whether or not a patient rated the pain intensity at NRS=10 within less than 45 s during the cold water immersion test provided a negative predictive value of 94.4% to assign a patient to the "persistent pain" group. If NRS=10 was never reached during the cold test, the predictive value for not developing persistent pain was almost 97%. However, a low negative predictive value of 10% implied a high false positive rate. Conclusion. Results provide a robust exclusion of persistent pain in women with an accuracy of 94.4%. Moreover, results provide further support for the hypothesis that the endogenous pain inhibitory system may play an important role in the process of pain becoming persistent.Peer reviewe

Goos-H\"anchen shifts in frustrated total internal reflection studied with wave packet propagation

We have investigated that the Goos-H\"anchen (GH) shifts in frustrated total internal reflection (FTIR) studied with wave packet propagation. In the first-order approximation of the transmission coefficient, the GH shift is exactly the expression given by stationary phase method, thus saturates an asymptotic constant in two different ways depending on the angle of incidence. Taking account into the second-order approximation, the GH shift always depends on the width of the air gap due to the modification of the beam width. It is further shown that the GH shift with second-order correction increases with decreasing the beam width at the small incidence angles, while for the large incidence angles it reveals a strong decrease with decreasing the beam width. These phenomena offers the better understanding of the tunneling delay time in FTIR.Comment: 4 pages, 3 figure

Control of Goos-Hanchen shift of a light beam via a coherent driving field

We present a proposal to manipulate the Goos-Hanchen shift of a light beam via a coherent control field, which is injected into a cavity configuration containing the two-level atomic medium. It is found that the lateral shifts of the reflected and transmitted probe beams can be easily controlled by adjusting the intensity and detuning of the control field. Using this scheme, the lateral shift at the fixed incident angle can be enhanced (positive or negative) under the suitable conditions on the control field, without changing the structure of the cavity.Comment: 12 pages, 5 figure

Phenyl-triazine oligomers for light-driven hydrogen evolution

The design of stable, yet highly tunable organic photocatalysts which orchestrate multi-step electron transfer reactions is at the heart of the newly emerging field of polymer photocatalysis. Covalent triazine frameworks such as the archetypal CTF-1 have been theorized to constitute a new class of photocatalytically active polymers for light-driven water splitting. Here, we revisit the ionothermal synthesis of CTF-1 by trimerization of 1,4-dicyanobenzene catalyzed by the Lewis acid zinc chloride and demonstrate that the microporous black polymer CTF-1 is essentially inactive for hydrogen evolution. Instead, highly photoactive phenyl-triazine oligomers (PTOs) with higher crystallinity as compared to CTF-1 are obtained by lowering the reaction temperature to 300 °C and prolonging the reaction time to >150 hours. The low reaction temperature of the PTOs largely prevents incipient carbonization and thus results in a carbon-to-nitrogen weight ratio close to the theoretical value of 3.43. The oligomers were characterized by MALDI-TOF and quantitative solid-state NMR spectroscopy, revealing variations in size, connectivity and thus nitrile-to-triazine ratios depending on the initial precursor dilution. The most active PTO samples efficiently and stably reduce water to hydrogen with an average rate of 1076 (±278) μmol h−1 g−1 under simulated sunlight illumination, which is competitive with the best carbon nitride-based and purely organic photocatalysts. The photocatalytic activity of the PTOs is found to sensitively depend on the polymerization degree, thus suggesting a prominent role of the unreacted nitrile moieties in the photocatalytic process. Notably, PTOs even show moderate hydrogen production without the addition of any co-catalyst

Ionothermal Synthesis of Imide-Linked Covalent Organic Frameworks

Covalent organic frameworks (COFs) are an extensively studied class of porous materials, which distinguish themselves from other porous polymers in their crystallinity and high degree of modularity, enabling a wide range of applications. COFs are most commonly synthesized solvothermally, which is often a time‐consuming process and restricted to well‐soluble precursor molecules. Synthesis of polyimide‐linked COFs (PI‐COFs) is further complicated by the poor reversibility of the ring‐closing reaction under solvothermal conditions. Herein, we report the ionothermal synthesis of crystalline and porous PI‐COFs in zinc chloride and eutectic salt mixtures. This synthesis does not require soluble precursors and the reaction time is significantly reduced as compared to standard solvothermal synthesis methods. In addition to applying the synthesis to previously reported imide COFs, a new perylene‐based COF was also synthesized, which could not be obtained by the classical solvothermal route. In situ high‐temperature XRPD analysis hints to the formation of precursor–salt adducts as crystalline intermediates, which then react with each other to form the COF

Thermal Conversion of Guanylurea Dicyanamide into Graphitic Carbon Nitride via Prototype CNx Precursors

Guanylurea dicyanamide, [(H2N)C(-O)NHC(NH2)2][N(CN)2], has been synthesized by ion exchange reaction in aqueous solution and structurally characterized by single-crystal X-ray diffraction (C2/c, a = 2249.0(5) pm, b = 483.9(1) pm, c = 1382.4(3) pm, β = 99.49(3)°, V = 1483.8(5) × 106 pm3, T = 130 K). The thermal behavior of the molecular salt has been studied by thermal analysis, temperature-programmed X-ray powder diffraction, FTIR spectroscopy, and mass spectrometry between room temperature and 823 K. The results were interpreted on a molecular level in terms of a sequence of thermally induced addition, cyclization, and elimination reactions. As a consequence, melamine (2,4,6-triamino-1,3,5-triazine) is formed with concomitant loss of HNCO. Further condensation of melamine yields the prototypic CNx precursor melem (2,6,10-triamino-s-heptazine, C6N7(NH2)3), which alongside varying amounts of directly formed CNxHy material transforms into layered CNxHy phases without significant integration of oxygen into the core framework owing to the evaporation of HNCO. Thus, further evidence can be added to melamine and its condensation product melem acting as “key intermediates” in the synthetic pathway toward graphitic CNxHy materials, whose exact constitution is still a point at issue. Due to the characteristic formation process and hydrogen content a close relationship with the polymer melon is evident. In particular, the thermal transformation of guanylurea dicyanamide clearly demonstrates that the formation of volatile compounds such as HNCO during thermal decomposition may render a large variety of previously not considered molecular compounds suitable CNx precursors despite the presence of oxygen in the starting material

Li₀.₆[Li₀.₂Sn₀.₈S₂] – a layered lithium superionic conductor

One of the key challenges of energy research is finding solid electrolytes with high lithium conductivities comparable to those of liquid electrolytes. In this context, developing new structural families of potential Li+ ion conductors and identifying structural descriptors for fast Li+ ion conduction to occur is key to expand the scope of viable Li+ ion conductors. Here, we report that the layered material Li0.6[Li0.2Sn0.8S2] shows a Li+ ion conductivity comparable to the currently best lithium superionic conductors (LISICONs). Li0.6[Li0.2Sn0.8S2] is composed of layers comprising edge-sharing Li/SnS6 octahedra, interleaved with both tetrahedrally and octahedrally coordinated Li+ ions. Pulsed field gradient (PFG) NMR studies on powder samples show intragrain (bulk) diffusion coefficients DNMR on the order of 10−11 m2 s−1 at room temperature, which corresponds to a conductivity σNMR of 9.3 × 10−3 S cm−1 assuming the Nernst–Einstein equation, thus putting Li0.6[Li0.2Sn0.8S2] en par with the best Li solid electrolytes reported to date. This is in agreement with impedance spectroscopy on powder pellets, showing a conductivity of 1.5 × 10−2 S cm−1. Direct current galvanostatic polarization/depolarization measurements on such samples show negligible electronic contributions (less than 10−9 S cm−1) but indicate significant contact resistance (d.c. conductivity in a reversible cell is 1.2 × 10−4 S cm−1 at 298 K). Our results suggest that the partial occupation of interlayer Li+ positions in this layered material is beneficial for its transport properties, which together with tetrahedrally coordinated Li sites provides facile Li+ ion diffusion pathways in the intergallery space between the covalent Sn(Li)S2 layers. This work therefore points to a generic design principle for new layered Li+ ion conductors based on the controlled depletion of Li+ ions in the interlayer space

Properties of Physical Systems: Transient Singularities on Borders and Surface Transitive Zones

Certain alternative properties of physical systems are describable by supports of arguments of response functions (e.g. light cone, borders of media) and expressed by projectors; corresponding equations of restraints lead to dispersion relations, theorems of counting, etc. As supports are measurable, their absolutely strict borders contradict the spirit of quantum theory and their quantum evolution leading to appearance of subtractions or certain needed flattening would be considered. Flattening of projectors introduce transitive zones that can be examined as a specification of adiabatic hypothesis or the Bogoliubov regulatory function in QED. For demonstration of their possibilities the phenomena of refraction and reflection of electromagnetic wave are considered; they show, in particular, the inevitable appearing of double electromagnetic layers on all surfaces that formerly were repeatedly postulated, etc. Quantum dynamics of projectors proves the neediness of subtractions that usually are artificially adding and express transient singularities and zones in squeezed forms.Comment: 12 p

Non symmorphic band degeneracy at the Fermi level in ZrSiTe

Non-symmorphic materials have recently been predicted to exhibit many different exotic features in their electronic structures. These originate from forced band degeneracies caused by the non-symmorphic symmetry, which not only creates the possibility to realize Dirac semimetals, but also recently resulted in the prediction of novel quasiparticles beyond the usual Dirac, Weyl or Majorana fermions, which can only exist in the solid state. Experimental realization of non-symmorphic materials that have the Fermi level located at the degenerate point is difficult, however, due to the requirement of an odd band filling. In order to investigate the effect of forced band degeneracies on the transport behavior, a material that has such a degeneracy at or close to the Fermi level is desired. Here, we show with angular resolved photoemission experiments supported by density functional calculations, that ZrSiTe hosts several fourfold degenerate Dirac crossings at the X point, resulting from non-symmorphic symmetry. These crossings form a Dirac line node along XR, which is located almost directly at the Fermi level and shows almost no dispersion in energy. ZrSiTe is thus the first real material that allows for transport measurements investigating Dirac fermions that originate from non-symmorphic symmetry.Comment: 13 pages, 4 figures, accepted for publication in New Journal of Physic