Atmospheric chemistry of diazomethane – an experimental and theoretical study

The kinetics of the O₃, OH and NO₃ radical reactions with diazomethane were studied in smog chamber experiments employing long-path FTIR and PTR-ToF-MS detection. The rate coefficients were determined to be k _CH2NN+O3?=?(3.2?±?0.4)?×?10^?17 and k _CH2NN+OH?=?(1.68?±?0.12)?×?10^?10 cm³ molecule^?1 s^?1 at 295?±?3?K and 1013?±?30 hPa, whereas the CH₂NN?+?NO₃ reaction was too fast to be determined in the static smog chamber experiments. Formaldehyde was the sole product observed in all the reactions. The experimental results are supported by CCSD(T*)-F12a/aug-cc-pVTZ//M062X/aug-cc-pVTZ calculations showing the reactions to proceed exclusively via addition to the carbon atom. The atmospheric fate of diazomethane is discussed.     

Trace Extensions,Determinant Bundles,and Gauge Group Cocycles

We study the geometry of determinant line bundles associated with Dirac operators on compact odd-dimensional manifolds. Physically, these arise as (local) vacuum line bundles in quantum gauge theory. We give a simplified derivation of the commutator anomaly formula using a construction based on noncyclic trace extensions and associated nonmultiplicative renormalized determinants.     

Molecular integrals over Gaussian-type geminal basis functions

We present formulas for the evaluation of molecular integrals over basis functions with an explicit Gaussian dependence on interelectronic coordinates. These formulas use expansions in Hermite Gaussian functions and represent an extension to the work of McMurchie and Davidson to two-electron basis functions. Integrals that depend on the coordinates of up to four electrons are discussed explicitly. A key feature of this approach is that it allows full exploitation of the shell structure of the orbital part of the basis. Received: 24 February 1997 / Accepted: 4 March 1997     

Escherichia coli single-stranded DNA-binding protein,a molecular tool for improved sequence quality in pyrosequencing

Pyrosequencing is a four-enzyme bioluminometric DNA sequencing technique based on a DNA sequencing by synthesis principle. Currently, the technique is limited to analysis of short DNA sequences exemplified by single-nucleotide polymorphism analysis. In order to expand the field for pyrosequencing, the read length needs to be improved and efforts have been made to purify reaction components as well as add single-stranded DNA-binding protein (SSB) to the pyrosequencing reaction. In this study, we have performed a systematic effort to analyze the effects of SSB by comparing the pyrosequencing result of 103 independent complementary DNA (cDNA) clones. More detailed information about the cause of low quality sequences on templates with different characteristics was achieved by thorough analysis of the pyrograms. Also, real-time biosensor analysis was performed on individual cDNA clones for investigation of primer annealing and SSB binding on these templates. Results from these studies indicate that templates with high performance in pyrosequencing without SSB possess efficient primer annealing and low SSB affinity. Alternative strategies to improve the performance in pyrosequencing by increasing the primer-annealing efficiency have also been evaluated.     

Neutron-induced fission cross section of 233Pa between 1.0 and 3.0 MeV

The energy dependent neutron-induced fission cross section of 233Pa has for the first time been measured directly with monoenergetic neutrons. This nuclide is an important intermediary in a thorium based fuel cycle, and its fission cross section is a key parameter in the modeling of future advanced fuel and reactor concepts. A first experiment resulted in four cross section values between 1.0 and 3.0 MeV, establishing a fission threshold in excess of 1 MeV. Significant discrepancies were found with a previous indirect experimental determination and with model estimates.     

Collective and two-quasiparticle states in 158Gd observed through study of radiative neutron capture in 157Gd

The level structure of ¹⁵⁸Gd has been studied using the prompt γ-rays and conversion electrons emitted following neutron capture in ¹⁵⁷Gd. The γ-ray energy and intensity measurements were made using both Ge(Li) detectors and a curved-crystal spectrometer. Conversion-electron energy and intensity measurements were made using two separate magnetic spectrometers: one to measure the primary electron spectrum and the other to measure the lower energy secondary electron spectrum. Some γ-γ coincidence measurements were also made among the secondary γ-rays. From these data, a neutron separation energy of 7937.1 ± 0.5 keV has been determined for ¹⁵⁸Gd. A level scheme containing 59 excited states with energies < 2.25 MeV, for which de-excitation modes have been identified, is proposed for ¹⁵⁸Gd. Many of these states have been grouped into rotational bands. A total of thirteen excited rotational bands with band-head energies below 2.0 MeV are contained in the level scheme. Features of the proposed level scheme include: the K^π = 0^?, 1^? and 2^? octupole-vibrational bands with band-head energies of 1263, 977 and 1793 keV, respectively; the γ-vibrational band at 1187 keV; three excited K^π = 0⁺ bands with band-head energies of 1196, 1452 and 1743 keV; several two-quasiparticle bands with band-head energies in keV (and K^π assignments) of 1380 (4⁺), 1636 (4^?), 1847 (1⁺), 1856 (1^?), 1920 (4⁺) and 1930 (1⁺). An analysis of (d, p) reaction data is presented which permits definite two-quasiparticle configuration assignments to be made to most of these latter bands. Evidence is presented which suggests strong mixing of some two-neutron and two-proton bands. A phenomenological four-band mixing analysis is made of the energy and E2 transition-probability data for the ground-state band and the three lowest-lying excited collective positive-parity bands. Good agreement with experiment is obtained. A Coriolis-mixing analysis of the octupole bands has been carried out and good agreement with the data on level energies and E1 transition probabilities to the ground-state band has been achieved. Values of Z, the ratio of the E1 transition matrix element with ΔK = 1 to that with ΔK = 0, involving the octupole bands and the first four 0⁺ bands are derived. For three of these 0⁺ bands, absolute values of these matrix elements are deduced. An interesting alternation in the sign of Z is observed for these four 0⁺ bands.     

Some transformation techniques with applications in global optimization

In this paper some transformation techniques, based on power transformations, are discussed. The techniques can be applied to solve optimization problems including signomial functions to global optimality. Signomial terms can always be convexified and underestimated using power transformations on the individual variables in the terms. However, often not all variables need to be transformed. A method for minimizing the number of original variables involved in the transformations is, therefore, presented. In order to illustrate how the given method can be integrated into the transformation framework, some mixed integer optimization problems including signomial functions are finally solved to global optimality using the given techniques.     

Measurements of absolute γ-ray intensities in the decays of very neutron rich isotopes of Cd and In

The half lives and the γ-ray branching ratios of neutron rich Cd and In isotopes have been investigated by simultaneous measurements of β- and γ-ray spectra. The results presented contain information on 21 different β-decaying isotopes or isomers of Cd and In in the mass region A=123–129. Four previously unknown or little known isotopes of Cd are reliably characterized for the first time.