Rotationally resolved S1-S0 electronic spectra of 2,6-diaminopyridine: a four-fold barrier problem

A comparison of the electronic properties of the nitrogen-containing rings aniline, 2-aminopyridine, and 2,6-diaminopyridine (26DAP) shows that the potential energy surface of the molecule is significantly affected as more nitrogen atoms are added to the system. High resolution, rotationally resolved spectra of four vibrational bands in the S(1)-S(0) electronic transition of 26DAP were obtained in order to explain these changes. The zig-zagging inertial defects point to a double minimum excited state potential energy surface along the coupled amino group inversion vibrational mode, which becomes a four-fold well (and barrier) problem when the existence of two nearly degenerate isomers is taken into account. Assuming that the molecules are in the lower energy, opposite-side configuration, ab initio calculations were performed using the MP2/6-31G** level of theory to create a potential energy surface modeling the simultaneous antisymmetric NH(2)-inversion mode. The calculated potential energy surface shows a ground electronic state barrier to simultaneous NH(2) inversion of ~220 cm(-1), and a fit to experimental vibrational energy level spacings and relative intensities produces an excited electronic state barrier of ~400 cm(-1). The ground state barrier is less than that in aniline, but the excited state barrier is larger.     

First-row transition metal atoms adsorption on rutile TiO2(110) surface

We performed periodic DFT calculations for adsorption of metal atoms on a perfect rutile TiO₂(110) surface (at low coverage, ???=?1/3) to investigate the interaction of an individual metal atom with TiO₂ and to compare it with a study previously done on MgO(100). We considered partial period of Mendeleev??s table from K to Zn. The overall evolution of the adsorption energies shows two maxima as for MgO(100). Two main differences, however, exist: the adsorption energy is much stronger and the first maximum is enhanced relative to the second one. This is attributed to the reducibility of the surface titanium cation. When the adsorbed metal is electropositive, it is oxidized under adsorption transferring electrons to titanium cations. We present the effect of introducing a Hubbard term to the gradient-corrected approximation band-structure Hamiltonian (GGA?+?U). The introduction of a reasonable Hubbard correction preserves the trends and allows localizing the electron of the reduction on Ti atoms in the near surface region. Finally, our results conclude that for heavier M atoms of the period, insertion is energetically favored relative to adsorption.     

Reaction of acetone oxime with dialkylmalonyl chlorides. Synthesis of 2-(2-propenyl)isoxazolidine-3,5-diones and 2,2-bis-(2-(4,4-dialkylisoxazolidine-3,5-dione))propanes

Reaction of acetone oxime with dialkylmalonyl chlorides in the presence of triethylamine gave as products 2-(2-propenyl)-4,4-dialkylisoxazolidine-3,5-diones 4 and 2,2-bis-(2-(4,4-dialkylisoxazolidine-3,5-dione))propanes 5 . The 4,4-dialkylisoxazolidine-3,5-diones 6 and dimethylketoximyl 4,4-dialkylmalonates 7 were formed as minor products. Compounds 4 are stable in refluxing ethanol and in aqueous solution. Compounds 5 are stable when heated in refluxing toluene in the presence of either pyridine or monochloroacetic acid.     

A convexity-preservingC 2 parametric rational cubic interpolation

Summary AC ² parametric rational cubic interpolantr(t)=x(t) i+y(t) j,t[t ₁,t _n] to data S={(x_j, y_j)|j=1,...,n} is defined in terms of non-negative tension parameters _j ,j=1,...,n–1. LetP be the polygonal line defined by the directed line segments joining the points (x _j ,y _j ),t=1,...,n. Sufficient conditions are derived which ensure thatr(t) is a strictly convex function on strictly left/right winding polygonal line segmentsP. It is then proved that there always exist _j ,j=1,...,n–1 for whichr(t) preserves the local left/righ winding properties of any polygonal lineP. An example application is discussed.This research was supported in part by the natural Sciences and Engineering Research Council of Canada.     

Wavelength dependence of picosecond absorption saturation in gallium arsenide

Absorption saturation in the picosecond regime has been observed in GaAs MBE-grown epitaxial layers at low temperature, and its wavelength dependence in the range 700–820 nm has been observed using 7 psec pulses from a tunable infrared LiIO₃ parametric generator. For peak intensities up to 1 GW cm^?2 almost complete saturation of band-to-band absorption could be achieved without damaging the sample. Although the direct saturation of optically coupled states is expected to become the dominant contribution in the ultrashort limit, our experimental results are quantitatively described with the band-filling model, which includes the dynamic Burstein shift and bandgap renormalization.     

Holdings of financial assets: A Markov chain analysis

This paper introduces the Markov chain model as a simple tool for analyzing the pattern of financial asset holdings over time. The model is based on transition probabilities which give the probability of switching $1 of wealth from one asset to another. An illustrative application is provided.     

Thermally induced vibrations of a viscoelastic plate

A method for the study of thermally induced vibrations of a viscoelastic plate of arbitrary shape is proposed. The method is based upon the concept of iso-amplitude contour lines on the surface of the plate. It is shown that the time behaviour can be found by assuming a normal mode expansion in terms of the eigenfunctions for the associated elastic plate problem, and the deflection is obtained by using the elastic-viscoelastic analogy. As an illustration of the technique, the vibration of a viscoelastic circular plate under a thermal shock at its centre is discussed, all details of which are illustrated by graphs.     

Letzte Entwicklungen in der Theorie und Praxis der dynamischen analytischen Technik (Continuous Flow Analysis)

Zusammenfassung Während der beiden letzten Jahre hat man versucht, eine theoretische Basis für die dynamische analytische Technik zu entwickeln. Neue Systeme, die auf diesen Überlegungen basieren, sind schon konstruiert und haben bessere Eigenschaften bewiesen. Zwei Systeme, die schon auf dem Markt sind, werden beschrieben. Das erste ist ein Vielfachanalysen-system, das für klinische Routineuntersuchungen vorgesehen ist. Das zweite ist ein neuer vollautomatischer Aminosäurenanalysator, welcher in der Lage ist, Chromatogramme viel schneller als jedes andere existierende Gerät zu produzieren.

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Latest developments in the theory and practice of continuous flow analysis

In the last few years there has been an increased interest in developing a theoretical basis for continuous flow analysis. These theoretical considerations have lead to the development of improved and simplified analytical systems. Two such systems are already commercially available and are described. The first is a multiple system for the routine clinical examination of blood serum for 12 different parameters. The second is a fully automated chromatographic system for the determination of amino acids in protein hydrolysates and physiological fluids.

     

Bistability and the phase transition in 1,3,2-dithiazolo[4,5-b]pyrazin-2-yl

The molecular radical 1,3,2-dithiazolo[4,5-b]pyrazin-2-yl (PDTA) exhibits magnetic bistability just above room temperature, undergoing a well-defined hysteretic phase change with TC downward arrow = 297(1) K and TC upward arrow = 343(1) K. The crystal structures of the two phases of PDTA have been determined by single-crystal X-ray diffraction at 323(2) K. LT-PDTA consists of diamagnetic (S = 0) nearly superimposed pi-dimer stacks, while that of HT-PDTA comprises slipped stacks of pi-radicals (S = 1/2). The structural interconversion is suggested to proceed via the cooperative breaking and making of intermolecular S- - -N interactions and an inversion symmetry-preserving "domino cascade" of the pi-stacked rings.     

Three-body dissociation dynamics of the low-lying Rydberg states of H3 and D3

The dynamics of the three-body dissociative charge exchange of fast (12 keV) H+3 and D+3 with Cs have been studied using multiparticle translational spectroscopy. The observed partitioning of product momenta was found to be state-specific and yields insights into the nuclear motion during dissociation for the three lowest-lying 2s 2A'1, 2p 2A'2, and 3p 2E' metastable Rydberg states of H3 and the 2s 2A'1 and 2p 2A'2 states for D3. These results provide direct empirical information on the nonadiabatic couplings that govern the three-body dissociation of the lowest-lying Rydberg states of H3 and D3.