Chaotic and periodic emission of high power solid state lasers

Nonlinear, dynamical systems even with a few degrees of freedom may show chaotic or periodic behaviour, depending on the parameters of the system. Recently it was demonstrated, both experimentally and theoretically, that the temporal emission of a laser can become chaotic, if several longitudinal modes oscillate [Brunner and Paul (1983), and Abraham et al. (1982)]. The chaotic emission is caused by the nonlinear interaction of the modes and the longitudinal gain structure [Komtomtseva et al. (1982)]. In this paper it is pointed out that the transverse mode structure and the radial gain profile produced by the transversal modes, may give rise to temporal instabilities of the laser emission. If the relevant parameters of the laser oscillator — Fresnel number, resonator losses, pump rate — exceed certain critical values, the output intensity becomes unstable. The damped relaxation oscillation changes into undamped periodic oscillation or, with increasing values of the above parameters, into chaotic emission. The theory, using the nonlinear Kirchhoff-Fresnel integral equation and the rate equation approach, is confirmed by experimental results.     

Kinetics and mechanism of proton transport across membrane nanopores

We use computer simulations to study the kinetics and mechanism of proton passage through a narrow-pore carbon-nanotube membrane separating reservoirs of liquid water. Free energy and rate constant calculations show that protons move across the membrane diffusively along single-file chains of hydrogen-bonded water molecules. Proton passage through the membrane is opposed by a high barrier in the effective potential, reflecting the large electrostatic penalty for desolvation and reminiscent of charge exclusion in biological water channels. At neutral pH, we estimate a translocation rate of about 1 proton per hour and tube.     

Cycloaddition Reactions of an Active Cyclic Phosphane/Borane Pair with Alkenes,Alkynes, and Carbon Dioxide

The active six-membered cyclo-FLP 6 undergoes a rapid P/B addition reaction to carbon dioxide. At elevated temperature, the resulting heterobicyclo[2.2.2]octane derived product 7 undergoes ring opening and equilibrates with the cyclotetramer (7)₄ . In the large macrocyclic structure, four monomeric six-membered cyclo-FLP units are connected by four CO₂ molecules to form the supramolecular ring system. The P/B cyclo-FLP 6 undergoes a variety of additional cycloaddition reactions.     

A hybrid Arnoldi-Faber iterative method for nonsymmetric systems of linear equations

Summary We present here a new hybrid method for the iterative solution of large sparse nonsymmetric systems of linear equations, say of the formAx=b, whereA ^{N, N} , withA nonsingular, andb ^N are given. This hybrid method begins with a limited number of steps of the Arnoldi method to obtain some information on the location of the spectrum ofA, and then switches to a Richardson iterative method based on Faber polynomials. For a polygonal domain, the Faber polynomials can be constructed recursively from the parameters in the Schwarz-Christoffel mapping function. In four specific numerical examples of non-normal matrices, we show that this hybrid algorithm converges quite well and is approximately as fast or faster than the hybrid GMRES or restarted versions of the GMRES algorithm. It is, however, sensitive (as other hybrid methods also are) to the amount of information on the spectrum ofA acquired during the first (Arnoldi) phase of this procedure.     

Internal rotation and chlorine nuclear quadrupole coupling of o-chlorotoluene studied by microwave spectroscopy and ab initio calculations

The microwave spectrum of o-chlorotoluene has been reinvestigated using molecular beam Fourier transform microwave (MB-FTMW) spectrometers in the frequency range of 4–23 GHz. Due to the high resolution of this molecular beam technique the analysis yielded improved rotational constants, centrifugal distortion constants, and, for the first time, the complete chlorine nuclear quadrupole coupling tensor. From the torsional fine structure the barrier to internal rotation of the methyl group was found to be 5.5798(52) kJ mol⁻¹. Experimental results and ab initio calculations are compared.     

Recent advances in capillary electrophoretic migration techniques for pharmaceutical analysis (2013–2015)

This review updates and follows‐up a previous review by highlighting recent advancements regarding capillary electromigration methodologies and applications in pharmaceutical analysis. General approaches such as quality by design as well as sample injection methods and detection sensitivity are discussed. The separation and analysis of drug‐related substances, chiral CE, and chiral CE‐MS in addition to the determination of physicochemical constants are addressed. The advantages of applying affinity capillary electrophoresis in studying receptor–ligand interactions are highlighted. Finally, current aspects related to the analysis of biopharmaceuticals are reviewed. The present review covers the literature between January 2013 and December 2015.     

Spectroscopic characterization of molybdenum dinitrogen complexes containing a combination of di- and triphosphine coligands: 31P NMR analysis of five-spin systems

The three molybdenum-N2 complexes [Mo(N2)(dpepp)(depe)] (1), [Mo(N2)(dpepp)(dppe)] (2), and [Mo(N2)(dpepp)(1,2-dppp)] (3), all of which contain a combination of a bi- and a tridentate phosphine ligand, were prepared and investigated by vibrational and (31)P NMR spectroscopy. As a tridentate ligand bis(2-diphenylphosphinoethyl)phenylphosphine (dpepp) has been employed. The three different bidentate ligands are 1,2-bis(diethylphosphino)ethane (depe), 1,2-bis(diphenylphosphino)ethane (dppe), and R-(+)-1,2-bis(diphenylphosphino)propane (1,2-dppp). N-N as well as metal-N vibrations of 1-3 are identified and interpreted in terms of the geometric and electronic structures of the complexes. (31)P NMR spectra are recorded and fully analyzed. Moreover, correlation spectroscopy (COSY)-45 measurements are performed to determine the relative signs of coupling constants. Special attention is directed to a detection of different isomers and their (31)P NMR, as well as vibrational spectroscopic properties. The implications of the results for the area of synthetic nitrogen fixation with phosphine complexes are discussed.     

Tandem cyclopropanation with dibromomethane under Grignard conditions

Tertiary Grignard reagents and dibromomethane efficiently cyclopropanate allylic (and certain homoallylic) magnesium and lithium alcoholates at ambient temperature in ether solvents. Lithium (homo)allyl alcoholates are directly cyclopropanated with magnesium and CH2Br2 under Barbier conditions at higher temperatures. The reaction rates depend on the substitution pattern of the (homo)allylic alcoholates and on the counterion with lithium giving best results. Good to excellent syn-selectivities are obtained from alpha-substituted substrates, which are in accord with a staggered Houk model. In tandem reactions, cyclopropyl carbinols are obtained from allyloxylithium or -magnesium intermediates, generated in situ by alkylation of conjugated aldehydes, ketones, and esters as well as from allyl carboxylates or vinyloxiranes. Using this methodology, numerous fragrance ingredients and their precursors were efficiently converted to the corresponding cyclopropyl carbinols.