Electronic spectroscopy and ionization potential of UO2 in the gas phase

The electronic spectroscopy of UO(2) has been examined using multiphoton ionization with mass-selected detection of the UO(2) (+) ions. Supersonic jet cooling was used to reduce the spectral congestion. Twenty-two vibronic bands of neutral UO(2) were observed in the range from 17,400 to 32,000 cm(-1). These bands originated from the U(5fphi(u)7ssigma(g))O(2) X (3)Phi(2u) and (3)Phi(3u) states. The stronger band systems are attributed to metal-centered 7p<--7s transitions. Threshold ionization measurements were used to determine the ionization potentials of UO and UO(2). These were found to be higher than the values obtained previously from electron impact measurements but in agreement with the results of recent theoretical calculations.     

Carbon-carbon coupling constants - a new guide in the stereochemistry of oximes

A positive contribution of more than 7 Hz to the direct ¹³C-¹³C spin-spin coupling constants induced by the proximity of the nitrogen lone pair in syn-orientation to the coupled nuclei allows an unambiguous configuration assignment of diverse oximes.     

Erosion of efficiency in non-uniform linear chromatography

In linear chromatography (i.e. chromatography performed in the absence of sample overloading), when the plate height of a column is roughly uniform along its length, variations in the velocities of solutes are the only possible causes of erosion of efficiency. The sources of these variations (variations in capacity ratio and in the density of the mobile phase, etc.) play no direct role in the erosion of efficiency except through their effect on solute velocities. In other words, what eventually causes the erosion of efficiency is merely variation in the time required for solutes to traverse equally small segments of a column. Significant erosion can only arise from abrupt and deep deceleration of solutes in one or several relatively small segments of a column. If erosion of efficiency caused by pressure gradients in linear SFC is to be large, the depth and the sharpness of the deceleration of a solute must go beyond that hitherto confirmed experimentally. Many relevant examples are analyzed graphically.     

Selective hydrodechlorination of fluorinated arylamines

Chlorine-containing polyfluorinated anilines and meta-phenylenediamines undergo selective hydrodechlorination easily upon reduction by zinc in aqueous ammonia. A new approach is thus provided to synthetically valuable, partially fluorinated arylamines based on utilizing polyfluorochloroarenes, which are available as intermediates of perfluoroarene production from perchloroarenes. When chlorine atoms are present in positions both ortho and para to the amino group, para chlorine is initially eliminated. Based on this reaction, a one-pot synthesis of partially fluorinated 4-aminopyridines from 3,5-dichlorotrifluoro- and 3-chlorotetrafluoropyridine has been realized.     

Adaptive efficient analysis for big data ergodic diffusion models

Statistical Inference for Stochastic Processes - We consider drift estimation problems for high dimension ergodic diffusion processes in nonparametric setting based on observations at discrete...     

Anisotropic<Emphasis Type="Italic">s</Emphasis>-wave or<Emphasis Type="Italic">d</Emphasis>-wave pairing? Analysis of experiments on ion irradiation of YBa<Subscript>2</Subscript>Cu<Subscript>3</Subscript>O<Subscript>7-x</Subscript> films

The effect of ion irradiation on the superconducting transition temperatureT _c and resistivityρ _ab (T) of YBa₂Cu₃O_7-x films with different oxygen content (initial temperatureT _c0≈90 K and 60 K) is studied experimentally. The dependenciesT _c /T _c0 on residual resistivityρ _o are obtained in very wide range 0.2<T _c /T _c0 <1 andρ _o μΩ·cm. The critical values ofρ _o , corresponding to the vanishing of superconductivity, are found to be an order of magnitude larger then those predicted by theory ford-wave pairing. At 0.5÷0.6<T _c /T _c0<1 the experimental data are in close agreement with theoretical dependencies, obtained for the anisotropics-wave superconductor within the BCS-framework.     

Approximate minimum-cost multicommodity flows in\tilde O(ɛ −2 KNM) timetime

We show that an ε-approximate solution of the cost-constrainedK-commodity flow problem on anN-nodeM-arc network,G can be computed by sequentially solving O(K(? ^?2+logGK) logGM log (G? ^?1 GK)) single-commodity minimum-cost flow problems on the same network. In particular, an approximate minimum-cost multicommodity flow can be computed in $\tilde O$ (G? ^?2 GKNM) running time, where the notation Õ(·) means “up to logarithmic factors”. This result improves the time bound mentioned by Grigoriadis and Khachiyan [4] by a factor ofM/N and that developed more recently by Karger and Plotkin [8] by a factor of? ^?1. We also provide a simple $\tilde O$ (NM)-time algorithm for single-commodity budget-constrained minimum-cost flows which is $\tilde O$ (? ^?3) times faster than the algorithm developed in the latter paper.     

Accurate ionization potentials for UO and UO2: a rigorous test of relativistic quantum chemistry calculations

Accurate ionization potential (IP) measurements provide essential thermodynamic information and benchmark data that can be used to evaluate the validity of electronic structure models. Calculations of the first IP of UO2 using relativistic methods consistently predict values that are approximately 0.7 eV higher than the accepted experimental value. The present measurements validate the theoretical calculations and show that the previous determinations corresponded to the ionization of thermally excited molecules. Similarly, new measurements of the IP for UO show that the currently accepted value is too low by 0.4 eV.