The AB2-XA1 electronic transition of NO2: A rovibronic survey covering 14 300-18 000 cm

More than 250 rotationally resolved vibrational bands of the A²B₂-X²A₁ electronic transition of ¹⁵NO₂ have been observed in the 14 300-18 000 cm⁻¹ range. The bands have been recorded in a recently constructed setup designed for high resolution spectroscopy of jet cooled molecules by combining time gated fluorescence spectroscopy and molecular beam techniques. The majority of the observed bands has been rotationally assigned and can be identified as transitions starting from the vibrational ground state or from vibrationally excited (hot band) states. An exceptionally strong band is located at 14 851 cm⁻¹ and studied in more detail as a typical benchmark transition to monitor ¹⁵NO₂ in atmospheric remote sensing experiments. Standard rotational fit routines provide band origins, rotational and spin rotation constants. A subset of 177 vibronic levels of ²B₂ vibronic symmetry has been analyzed in the energy range between 14 300 and 17 250 cm⁻¹, in terms of integrated density and using Next Neighbor Distribution. It is found that the overall statistical properties and polyad structure of ¹⁵NO₂ are comparable to those of ¹⁴NO₂ but that the internal structures of the polyads are completely different. This is a direct consequence of the X²A₁-A²B₂ vibronic mixing.     

Determination of the partial electron capture- and spontaneous-fission half-lives of254No

The isotope²⁵⁴No was produced in the fusion reaction⁴⁸Ca +²⁰⁸Pb. Using the velocity filter SHIP and radiochemical techniques it was found that the nuclide²⁵⁴No with a half-life of 55 s decays byα, EC, and spontaneous-fission. Deduced partial half-lives are (61±2) s forα-decay, (550 _?160 ⁺³⁷⁰ ) s for EC and [2.2 _?1.0 ^+2.0 ]×10⁴ s for spontaneous fission.     

Averaged molecular weight of complex mixtures as determined by rapid measurements of diffusion

Summary The concept of a diffusion-averaged molecular weight, M_d is presented, and M_d is defined for polydisperse samples. It is shown via oligostyrene mixtures that M_d can be determined in 20 minutes with common chromatographic equipment. If M_d is measured and M_n or M_w is known, the polydispersity can be obtained.     

Über Pterinchemie. 49. Mitteilung. Eine neue Synthese von 5-Formyl-6, 7-dimethyl-5,6,7,8-tetrahydropterin und 5,6,7-Trimethyl-5,6,7,8-tetrahydropterin

Starting with 5-formyl-6,7-dimethyl-5,6,7,8-tetrahydropterine (II), a new synthesis of 5,6,7-trimethyl-5,6,7,8-tetrahydropterine (III) is described. Thereby the chemical behaviour of the 5-formyl group in II is investigated, in order to enable the unequivocal differentiation between formylation at position 5 and at position 10 in folic and tetrahydrofolic acid derivatives. ¹³C-NMR. spectra of II and III are discussed.     

Über Pterinchemie. 79. Mitteilung. 13C-und 15N-NMR.-spektroskopische Untersuchungen an der (6RS)-5, 10-Methylen-5, 6, 7, 8-tetrahydro-L-folsäure; eindeutiger Beweis ihrer Struktur

¹³C- and ¹⁵N-NMR.-Spectroscopic Studies on (6RS)-5, 10-Methylene-5, 6, 7, 8-tetrahydro-L -folic Acid; Unequivocal Proof of thier Structure The existence of a 5, 10-methylene bridge in the title compound has been established with the help of ¹⁵N-NMR, and ¹³C-NMR. spectroscopy. The simultaneous coupling of ¹³C(11) with ¹⁵N(5) and ¹⁵N(10) proves that C(11) must be bound as a methylene bridge to both N-atoms. Some other aspects of the NMR. spectra of the compound are discussed. Synthesis of the title product with the label ¹⁵N is described.     

Über Pterinchemie. Mitteilung. Die Kristallstruktur von 5,6,7-Trimethyl-5,6,7,8-tetrahydropterindihydrochlorid-monohydrat

The crystal structure of 5,6,7-trimethyl-5,6,7,8-tetrahydropterine-dihydrochloride-monohydrate The crystal structure of the title compound has been determined by X-ray analysis (direct methods) and refined with 947 structure amplitudes to R = 0.026. The crystal system is orthorhombic, space group Pna2₁, with unit cell dimensions a = 14.081, b = 14.623, c = 6.773 Å. The molecule is protonated at the N(1)- and N(5)-position. The tetrahydropyrazine ring exists in a conformation in which C(6) deviates markedly from the mean plane of the other five atoms. The CH₃-groups at N(5) and C(6) possess a trans configuration with a pseudoaxial and an axial conformation respectively. The CH₃-groups at C(6) and C(7) in return possess the cis configuration, whereby the CH₃-group at C(7) occupies an equatorial conformation.     

(Benzylthio)- und (Arylthio)-substituierte Nitril-ylide: Thermische Erzeugung und Reaktionen

Thermal Generation and Reactions of (Benzylthio)-and (Arylthio)-Substituted Nitrile Ylides Thermolysis of 4-(benzylthio)- and 4-(arylthio)-1,3-oxazol-5(2H)-ones 6 , at 110–155° in the presence of dipolarophiles with activated C≡C, C?C, C?O, C?S, and N?N bonds, led to 5-membered cyclo-adducts and CO² (cf. Schemes 3, 5-7). Heating 6a and 6c in the presence of ethyl propiolate yielded ethyl quinoline-3-carboxylate ( 19 ) and ethyl pyridine-3-carboxylate( 22 ), respectively (cf. Scheme 8). These results are rationalized on the basis of the intermediate formation of thio-substituted nitrile ylides of type 7 (cf. Scheme 2), which undergo regioselective 1,3-dipolar cycloadditions with reactive dipolarophiles. In the absence of such a dipolarophile, the nitrile ylides isomerize via a [1,4]-H shift to give 2-aza-1,3-butadienes of type 20 . The latter are trapped in a Diels-Alder reaction with ethyl propiolate (cf. Scheme 8).     

Jet cooled NO2 intra cavity laser absorption spectroscopy (ICLAS) between 11200 and 16150 cm

We have combined the high sensitivity of the ICLAS technique with the rotational cooling effect of a slit jet expansion in order to observe and to understand the visible and near infrared NO₂ spectrum. By this way, an equivalent absorption pathlength of several kilometers through rotationally cooled molecules has been achieved. Due to the vibronic interaction between the two lowest electronic states, ²A₁ and à ²B₂, this spectrum is vibronically dense and complex. Moreover, the dense room temperature rotational structure is perturbed by additional rovibronic interactions. In contrast, the rotational analysis of our jet cooled spectrum is straightforward. The NO₂ absorption spectrum is vanishing to the IR but, owing to the high sensitivity of the ICLAS technique, we have been able to record the NO₂ spectrum down to 11200 cm⁻¹ with a new Ti:sapphire ICLAS spectrometer. As a result 249 ²B₂ vibronic bands have been observed (175 cold bands and 74 hot bands) in the 11200–16150 cm⁻¹ energy range. Due to the cooling effect of the slit jet we have reduced the rotational temperature down to about 12 K and at this temperature the K = 0 subbands are dominant. Consequently, we have analysed only the K = 0 manifold for N 7 of each vibronic band. The dynamical range of the band intensities is about one thousand. Due to the strong vibronic interaction between the ²A₁ and à ²B₂ electronic states, we observed not only the a₁ vibrational levels of the à ²B₂ state but also the b₂ vibrational levels of the ²A₁ state interacting with the previous ones. By comparison with the calculated density of states, we conclude that we have observed about 65% of the total number of ²B₂ vibronic levels located in the studied range. However, there are more missing levels in the IR because of the weakness of the spectrum in this range. The correlation properties of this set of vibronic levels have been analysed calculating the power spectrum of the absorption stick spectrum which displays periodic motions: the dominant period, at 714 ± 20 cm⁻¹, corresponds to the bending motion of the à ²B₂ state. The other observed periods remain unassigned. In contrast the next neighbor spacing distribution (NNSD) shows a strong level repulsion, i.e. a manifestation of quantum chaos. These two observations, apparently contradictory, can be rationalized as follows: the short time dynamics, for t < 10⁻¹² s, is “regular” while for longer times the dynamics becomes “chaotic”. We suggest that this behavior may be observed directly with a pump and probe fs laser experiment.     

Variational aspects of the Seiberg-Witten functional

The Seiberg-Witten equations that have recently found important applications for four-dimensional geometry are the Euler-Lagrange equations for a functional involving a connection A on a line bundleL and a section of another bundleW ⁺ constructed fromL and a spinor bundle on a given four-dimensional Riemannian manifold. We show the regularity of weak solutions and the Palais-Smale condition for this functional.