HCl and DCl: a case study of different approaches for determining photo fractionation constants

The photoabsorption cross sections of HCl and DCl are calculated using the reflection principle and time dependent wavepacket propagation methods. The absorption cross sections are compared to high precision experimental absorption cross sections from the literature and the different results given by the methods are discussed. The results of the calculations emphasize the important roles that photodissociation dynamics and the change in transition dipole moment with internuclear distance play in isotopic fractionation. The wave number dependent fractionation constants have been determined. The process fractionation constant has been calculated in the Venusian atmosphere where photo-fractionation leads to enrichment in deuterium through loss of hydrogen to space. At an altitude of 70 km the process fractionation constant was found to be epsilon(p) = -344 per thousand and epsilon(p) = -256 per thousand for the experimental and the reflection principle methods, respectively. At the top of the atmosphere the process fractionation constant was evaluated to be epsilon(p) = -32 per thousand, epsilon(p) = -20 per thousand and epsilon(p) = -40 per thousand using the experimental data, the wavepacket and the reflection principle methods, respectively. Using the Rayleigh distillation formula it is concluded that HCl at the top of the Venusian atmosphere is fractionated (enriched in D) relative to the bulk composition prior to photolysis.     

Nanosecond-Flash 15N Photo-CIDNP MAS NMR on Reaction Centers of Rhodobacter sphaeroides R26

Photochemically induced dynamic nuclear polarization (photo-CIDNP) is observed with time-resolved ¹⁵N magic-angle spinning (MAS) nuclear magnetic resonance (NMR) in uniformly ¹⁵N-labeled reaction centers (RCs) of the purple bacterium Rhodobacter (Rb.) sphaeroides R26 under illumination with nanosecond laser flashes. The ¹⁵N NMR signals enhanced by the solid-state photo-CIDNP effect are related to electron spin densities in the primary radical pair and allow for reconstruction of the electronic structure at atomic scale. New assignments for the photochemically active nitrogens are proposed based on simulations of the intensities. The ratio of electron spin densities between cofactors P _L and P _M is observed to be about 4:1. The origin of the high asymmetry is discussed.     

Normalized LMS digital filter for chromatic dispersion equalization in 112-Gbit/s PDM-QPSK coherent optical transmission system

High bit rates optical communication systems pose the challenge of their tolerance to linear and non-linear fiber impairments. Coherent optical receivers using digital signal processing techniques can mitigate the fiber impairments in the optical transmission system, including the chromatic dispersion equalization with digital filters. In this paper, an adaptive finite impulse response filter employing normalized least mean square algorithm is developed for compensating the chromatic dispersion in a 112-Gbit/s polarization division multiplexed quadrature phase shift keying coherent communication system, which is established in the VPI simulation platform. The principle of the adaptive normalized least mean square algorithm for signal equalization is analyzed theoretically, and at the meanwhile, the taps number and the tap weights in the adaptive finite impulse response filter for compensating a certain fiber chromatic dispersion are also investigated by numerical simulation. The chromatic dispersion compensation performance of the adaptive filter is analyzed by evaluating the behavior of the bit-error-rate versus the optical signal-to-noise ratio, and the compensation results are also compared with other present digital filters.     

Simulations of petawatt-class few-cycle optical-parametric chirped-pulse amplification, including nonlinear refractive index effects

We present three-dimensional simulations of optical-parametric chirped-pulse amplification stages for a few-cycle petawatt-class laser. The simulations take into account the effects of depletion, diffraction, walk-off, quantum noise, and the nonlinear refractive index (n(2)). In the absence of n(2) effects, we show these stages can generate 3.67J pulses supporting 4fs transform-limited pulse durations. Adding the nonlinear refractive index to the simulation, the energy output is reduced by ~11% and the bandwidth narrows by ~129nm, increasing the Fourier limit by ~17.5%.     

Covering homology

We introduce the notion of covering homology of a commutative S-algebra with respect to certain families of coverings of topological spaces. The construction of covering homology is extracted from Bökstedt, Hsiang and Madsen's topological cyclic homology. In fact covering homology with respect to the family of orientation preserving isogenies of the circle is equal to topological cyclic homology. Our basic tool for the analysis of covering homology is a cofibration sequence involving homotopy orbits and a restriction map similar to the restriction map used in Bökstedt, Hsiang and Madsen's construction of topological cyclic homology.Covering homology with respect to families of isogenies of a torus is constructed from iterated topological Hochschild homology. It receives a trace map from iterated algebraic K-theory and there is a hope that the rich structure, and the calculability of covering homology will make it useful in the exploration of J. Rognes' “red shift conjecture”.     

A low-temperature high-pressure apparatus with a temperature control system

Abstract

A low-temperature high-pressure apparatus was designed using commercial cryogenic equipment. Pressures up to 1 GPa and temperatures down to 40 K can be obtained in a volume of up to 30 cm³. The apparatus is of the piston-cylinder type with a piston diameter of 45 mm, and the pressure can be varied at all temperatures, An adaptive temperature control system keeps the temperature inside the pressure cylinder constant to within ±0.1 K.     

An independent set approach for the communication network of the GPS III system

In this article, we describe an algorithm to find the optimal communication network for the new GPS III satellite system. Finding a possible network will be translated to a maximum clique problem and an efficient algorithm for finding all maximum cliques under these special circumstances is described.     

Pyridyl Radical Cation for C−H Amination of Arenes

Electron‐transfer photocatalysis provides access to the elusive and unprecedented N‐pyridyl radical cation from selected N‐substituted pyridinium reagents. The resulting C(sp²)?H functionalization of (hetero)arenes furnishes versatile intermediates for the development of valuable aminated aryl scaffolds. Mechanistic studies that include the first spectroscopic evidence of a spin‐trapped N‐pyridyl radical adduct implicate SET‐triggered, pseudo‐mesolytic cleavage of the N?X pyridinium reagents mediated by visible light.     

Using magnetic core‐shell nanoparticles coated with an ionic liquid dispersion assisted by effervescence powder for the micro‐solid‐phase extraction of four beta blockers from human plasma by ultra high performance liquid chromatography with mass spectrometry detection

In this work, a novel, efficient, and green sorbent, SiO₂@Fe₃O₄ has been created and functionalized with 1‐butyl‐3‐methylimidazolium hexafluorophosphate as an ionic liquid. This sorbent was applied for microextraction of four beta blockers, propranolol, metoprolol, atenolol, and alprenolol with bupivacaine as internal standard from human plasma followed by liquid chromatography with mass spectrometric detection. A mixture of sodium bicarbonate and sodium dihydrogen phosphate was used as an extractant dispersive agent (effervescent power) to enhance the interaction between the magnetic sorbent and analytes. Main affecting parameters on microextraction and elution were optimized. Figures of merit for dispersive solid phase extraction with ionic liquid coated magnetic nanoparticles assisted by effervescent powder were calculated under the optimized conditions. The detection limits for propranolol, metoprolol, atenolol, and alprenolol were found at 0.33, 0.62, 0.03, and 0.44 ng/mL, respectively. For all analytes, good linearity was obtained. Intra‐ (n = 5) and interday (n = 10) precision were both under 6.3% while the preconcentration factors were obtained in the range between 15–18. The extraction efficiencies for each analyte ranged from 75 to 91%. The method was successfully applied for determination of trace amounts of the beta blockers in human plasma samples.