Quantum quench in the transverse-field Ising chain

We consider the time evolution of observables in the transverse-field Ising chain after a sudden quench of the magnetic field. We provide exact analytical results for the asymptotic time and distance dependence of one- and two-point correlation functions of the order parameter. We employ two complementary approaches based on asymptotic evaluations of determinants and form-factor sums. We prove that the stationary value of the two-point correlation function is not thermal, but can be described by a generalized Gibbs ensemble (GGE). The approach to the stationary state can also be understood in terms of a GGE. We present a conjecture on how these results generalize to particular quenches in other integrable models.     

High average power large-pitch fiber amplifier with robust single-mode operation

Ytterbium-doped large-pitch fibers with very large mode areas are investigated in a high-power fiber amplifier configuration. An average output power of 294?W is demonstrated, while maintaining robust single-mode operation with a mode field diameter of 62?μm. Compared to previous active large-mode area designs, the threshold of mode instabilities is increased by a factor of about 3.     

High-speed modal decomposition of mode instabilities in high-power fiber lasers

A high-speed mode analysis technique is required to gain fundamental understanding of mode instabilities in high-power fiber laser systems. In this work a technique, purely based on the intensity profile of the beam, is demonstrated to be ideally suited to analyze fiber laser dynamics. This technique, together with a high-speed camera, has been applied to the study of the temporal dynamics of mode instabilities at high average powers with up to 20,000 frames per second. These measurements confirm that energy transfer between the fluctuating transversal modes takes place in millisecond-time-scale.     

Crystalline Pr:SrAl12O19 waveguide laser in the visible spectral region

We fabricated waveguides in Pr:SrAl(12)O(19) crystals by direct femtosecond laser writing. The propagation losses were calculated to be as low as 0.16 dB/cm at a wavelength of 633 nm. Laser oscillation in a diode-pumped waveguide at a wavelength of 643.5 nm was realized. The output power of the waveguide laser was 28.1 mW at a slope efficiency of 8%.     

The Search for Highly Colored Organic Compounds

Until now the study of organic compounds in which the π-electron system is excited by absorbed light has been mainly concentrated on the ultraviolet and visible regions of the electromagnetic spectrum. Various new applications, such as the use of conjugated organic compounds as dye lasers or as materitals for storing information with the help of diode lasers, led to the synthesis of new compounds which absorb light in the near in infrared (NIR). It is possible to use structure-color relationships to predict the properties of such new compounds when they belong to dyestuff classes which have already been studied in detail; in this case the approach involves decreasing the energy difference between the ground state and the first excited state. A less conventional starting point is provided by molecular structures in which from the outset there is only a very small energy difference between the lowest-energy electronic states; such diradicaloid molecules occupy a special position among the various types of organic compounds. It is possible by means of suitable structural modification to stabilize such molecules in a singlet from which absorbs light at very long wavelengths (i.e. at small wave numbers).     

{[CuSn5Sb3]2−}2: A Dimer of Inhomogeneous Superatoms

Reaction of the binary Zintl anion (Sn₂Sb₂)^2? with the β‐diketiminato complex [LCu(NCMe)] (L=nacnac=[(N(C₆H₃ⁱPr₂‐2,6)C(Me))₂CH]^?) in ethylenediamine or DMF affords the ternary cluster dimer {[CuSn₅Sb₃]^2?}₂ ( 1 ) as its [K(crypt‐222)]⁺ salt. The chemical formulation of 1 is supported by energy‐dispersive X‐ray spectroscopy (EDX) and quantum chemical calculations. Each monomeric part of the dimer represents a trimetallic “[CuSn₅Sb₃]^2?” cluster, with an architecture in between a tricapped trigonal prism and a capped square antiprism. As shown by quantum chemical investigations, the presence of Sb atoms and, in particular, of Cu atoms in the cluster skeleton makes the monomeric unit behave like an inhomogeneous superatom, which clearly prefers to dimerize, thereby producing a relatively short, yet virtually non‐bonding Cu???Cu distance.     

Absolute configuration in 4-alkyl- and 4-aryl-3,4-dihydro-2(1H)-pyrimidones: a combined theoretical and experimental investigation

Structural features (orientation of the carboxyl group, ring puckering), electronic absorption, and circular dichroism spectra of 4-alkyl- and 4-aryl-dihydropyrimidones 1-5 are calculated by semiempirical (AM1, INDO/S), ab initio (HF/6-31G, CIS/6-31G, RPA/6-31G), and density functional theory (B3LYP/6-31G) methods. These calculations allow an assignment of the absolute configuration by comparison of simulated and experimental CD spectra. Although the ab initio methods greatly overestimate electronic transition energies, the general appearance of the experimental CD spectra is quite nicely reproduced by these calculations. Thus, comparison of experimental with calculated CD spectra is a reliable tool for the assignment of the absolute configuration. For 4-methyl derivatives 1, the first enantiopure DHPM examples with no additional aromatic substituent, the stereochemistry at C4 provided by the theoretical results is confirmed by X-ray structure determination of the diastereomeric salt 6. Additional support is the consistent HPLC elution order found for all investigated DHPMs on a cellulose-derived chiral stationary phase.     

MO-LCAO-Berechnungen an schwefelhaltigen π-Elektronensystemen

Zusammenfassung Mercaptosubstituierte Ionen von Schwefelheterocyclen, die iso--elektronisch mit dem Mercaptotropyliumion sind, zeigen mehrere charakteristische Absorptionsmaxima im Ultravioletten, die sich mehr oder weniger von den Absorptionen der unsubstituierten Heterocyclen unterscheiden. Diese Verbindungen werden durch Protonierung iso--elektronischer Thiotropene erhalten. Halbempirische SCF-LCI-Rechnungen mit früher abgeleiteten Parametern geben die experimentellen Ergebnisse gut wieder. Der Einfluß einer Methylsubstitution am exocyclischen Schwefel läßt sich durch eine Änderung des Parameters U _s abschätzen.

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MO-LCAO-calculations on sulfur containing -electron systemsXX. PPP-calculations on the mercapto-tropylium ion and iso--electronic sulfur-heterocycles

Iso--electronic thiotropones are converted by means of protonisation into mercaptosubstituted ions of the analogous heterocycles. These ions show various characteristic absorption maxima in the UV-region. Semiempirical SCF-LCI-calculations using parameters derived formerly reflect the experimental results satisfactory. By appropriate adjustment of the parameter U _s it is possible to estimate the influence of methyl substitution on the exocyclic sulfur atom.

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Résumé Des thiotropones isolélectroniques sont par protonation converties en ions mercapto-substitués des hétérocycles correspondants. Ces ions présentent différents maxima d'absorption caractéristiques dans le spectre U.V. Des calculs semi-empiriques SCF-LCI, utilisant des paramètres précédemment obtenus, reflètent d'une manière satisfaisante les résultats expérimentaux. Par un ajustement convenable du paramètre U _s il est possible d'estimer l'influence de la substitution méthylique sur l'atome de soufre exocyclique.

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19. Mitteilung: Hartmann, H., u. J. Fabian (im Druck).     

Manganese‐Catalyzed Dehydrogenative Alkylation or α‐Olefination of Alkyl‐Substituted N‐Heteroarenes with Alcohols

Catalysis with earth‐abundant transition metals is an option to help save our rare noble‐metal resources and is especially interesting when novel reactivity or selectivity patterns are observed. We report here on a novel reaction, namely the dehydrogenative alkylation or α‐olefination of alkyl‐substituted N‐heteroarenes with alcohols. Manganese complexes developed in our laboratory catalyze the reaction with high efficiency whereas iron and cobalt complexes stabilized by the same ligands are essentially inactive. Hydrogen is liberated during the reaction, and bromine and iodine functional groups as well as olefins are tolerated. A variety of alkyl‐substituted N‐heteroarenes can be functionalized, and benzylic and aliphatic alcohols undergo the reaction.