Family of Mixed-Valence Oxovanadium(IV/V) Dinuclear Entities Incorporating N4O3-Coordinating Heptadentate Ligands: Synthesis, Structure, and EPR Spectra

Dinuclear ((VVV)-V-IV) oxophenoxovanadates of general formula [V2O3L] have been synthesized in excellent yields by reacting bis(acetylacetonato)oxovanadium(IV) with H3L in a 2:1 ratio in acetone under an N-2 atmosphere. Here L3- is the deprotonated form of 2,6-bis[{{(2-hydroxybenzyl)(N',N'-(dimethylamino)ethyl)}amino}methyl]-4-methylphenol (H3L1), 2,6-bis[{{(5-methyl-2-hydroxybenzyl)(N',N'-(dimethylamino)ethyl)}amino}methyl]-4-methylphenol (H3L2) 2,6-bis[ {{(5-tert-butyl-2-hydroxybenzyl)(N',N'-(dimethylamino)ethyl)}amino}methyl]-4-methylphenoI (H3L3), 2,6-bis[{{(5-chloro-2-hydroxybenzyl)(N',N'-(dimethylamino)ethyl)}amino}methyl]-4-methylphenol (H3L4) , 2,6-bis[{{(5-bromo-2-hydroxybenzyl)(N',N'-(dimethylamino)ethyl)}amino}methyl]-4-methylphenol (H3L5), or 2,6-bis[{{(5-methoxy-2-hydroxybenzyl)(N',N'-(dimethylamino)ethyl)}amino}methyl]-4-methylphenol (H3L6). In [V2O3L1], both the metal atoms have distorted octahedral geometry. The relative disposition of two terminal V=O groups in the complex is essentially cis. The O=V...V=O torsion angle is 24.6(2)degrees. The V-O-oxo-V and V-O-phenoxo-V angles are 117.5(4) and 93.4(3)degrees, respectively. The V...V bond distance is 3.173(5) Angstrom. X-ray crystallography, IR, UV-vis, and H-1 and V-51 NMR measurements show that the mixed-valence complexes contain two indistinguishable vanadium atoms (type 111). The thermal ellipsoids of O2, O4, C10, C14, and C15 also suggests a type III complex in the solid state. EPR spectra of solid complexes at 77 K display a single line indicating the localization of the odd electron (3d(xy)(1)). Valence localization at 77 K is also consistent with the V-51 hyperfine structure of the axial EPR spectra (3d(xy)(1) ground state) of the complexes in frozen (77 K) dichloromethane solution: S = 1/2, g(parallel to) similar to 1.94, g(perpendicular to) similar to 1.98, A(parallel to) similar to 166 x 10(-4) cm(-1), and A(perpendicular to) similar to 68 x 10(-4) cm(-1). In contrast isotropic room-temperature solution spectra of the family have 15 hyperfine lines (g(iso) similar to 1.974 and A(iso) similar to 50 x 10(-4) cm(-1)) revealing that the unpaired electron is delocalized between the metal centers. Crystal data for the [V2O3L1].CH2Cl2 complex are as follows: chemical formula, C32H43O6N4C12V2; crystal system, monoclinic; space group, C2/c; a = 18.461(4), b = 17.230(3), c = 13.700(3) Angstrom; beta = 117.88(3)degrees; Z = 8.

Benedict-Webb-Rubin equation of state constants for N2O4 ⇄ 2NO2,NO,and O2

Benedict-Webb-Rubin equation of state constants for NO, O2, and the equilibrium mixture N2O4 ⇄ 2NO2 are reported.

Measurement of the WW+WZ Production Cross Section Using the lepton+jets Final State at CDF II

We report two complementary measurements of the WW+WZ cross section in the final state consisting of an electron or muon, missing transverse energy, and jets, performed using p\bar{p} collision data at sqrt{s} = 1.96 TeV collected by the CDF II detector. The first method uses the dijet invariant mass distribution while the second more sensitive method uses matrix-element calculations. The result from the second method has a signal significance of 5.4 sigma and is the first observation of WW+WZ production using this signature. Combining the results gives sigma_{WW+WZ} = 16.0 +/- 3.3 pb, in agreement with the standard model prediction.

Toward a widely usable finite-state morphology workbench for less studied languages, 1: Desiderata

Most of the world’s languages lack electronic word form dictionaries. The linguists who gather such dictionaries could be helped with an efficient morphology workbench that adapts to different environments and uses. A widely usable workbench could be characterized, ideally, as generally applicable, extensible, and freely available (GEA). It seems that such a solution could be implemented in the framework of finite-state methods. The current work defines the GEA desiderata and starts a series of articles concerning these desiderata in finite- state morphology. Subsequent parts will review the state of the art and present an action plan toward creating a widely usable finite-state morphology workbench.

Of citizen's rights and wrongs of the state

Argues that a human rights based concsiousness needs to supersede legal technocracy to avoid the wrongs of deporting family members. Response to public discussion over deportation of two elderly grandmothers from Finland.

A class of one-dimensional steady-state flows in radiation-gas-dynamics

The study of steady-state flows in radiation-gas-dynamics, when radiation pressure is negligible in comparison with gas pressure, can be reduced to the study of a single first-order ordinary differential equation in particle velocity and radiation pressure. The class of steady flows, determined by the fact that the velocities in two uniform states are real, i.e. the Rankine-Hugoniot points are real, has been discussed in detail in a previous paper by one of us, when the Mach number M of the flow in one of the uniform states (at x=+∞) is greater than one and the flow direction is in the negative direction of the x-axis. In this paper we have discussed the case when M is less than or equal to one and the flow direction is still in the negative direction of the x-axis. We have drawn the various phase planes and the integral curves in each phase plane give various steady flows. We have also discussed the appearance of discontinuities in these flows.

Search for WW and WZ production in lepton plus jets final state at CDF

We present a search for WW and WZ production in final states that contain a charged lepton (electron or muon) and at least two jets, produced in sqrt(s) = 1.96 TeV ppbar collisions at the Fermilab Tevatron, using data corresponding to 1.2 fb-1 of integrated luminosity collected with the CDF II detector. Diboson production in this decay channel has yet to be observed at hadron colliders due to the large single W plus jets background. An artificial neural network has been developed to increase signal sensitivity, as compared with an event selection based on conventional cuts. We set a 95% confidence level upper limit of sigma_{WW}* BR(W->lnu,W->jets)+ sigma_{WZ}*BR(W->lnu,Z->jets)

First Observation of Vector Boson Pairs in a Hadronic Final State at the Tevatron Collider

We present the first observation in hadronic collisions of the electroweak production of vector boson pairs (VV, V=W, Z) where one boson decays to a dijet final state. The data correspond to 3.5  fb-1 of integrated luminosity of pp̅ collisions at √s=1.96  TeV collected by the CDF II detector at the Fermilab Tevatron. We observe 1516±239(stat)±144(syst) diboson candidate events and measure a cross section σ(pp̅ →VV+X) of 18.0±2.8(stat)±2.4(syst)±1.1(lumi)  pb, in agreement with the expectations of the standard model.

First Observation of Vector Boson Pairs in a Hadronic Final State at the Tevatron Collider

We present the first observation in hadronic collisions of the electroweak production of vector boson pairs (VV, V=W,Z) where one boson decays to a dijet final state . The data correspond to 3.5 inverse femtobarns of integrated luminosity of ppbar collisions at sqrt(s)=1.96 TeV collected by the CDFII detector at the Fermilab Tevatron. We observe 1516+/-239(stat)+/-144(syst) diboson candidate events and measure a cross section sigma(ppbar->VV+X) of 18.0+/-2.8(stat)+/-2.4(syst)+/-1.1(lumi) pb, in agreement with the expectations of the standard model.

A Comparative Study of Aromaticity in Substituted Tetracyclic and Hexacyclic Thiophenes

We have studied the nature of aromaticity in expanded porphyrinic analogues of thiophenes formed by four and six thiophenes. Using density functional theory (DFT) we have analyzed the aromaticity of both the macrocycle and individual molecular fragments. We find paramagnetic annulenic ring currents in the case of tetracyclic molecules and diamagnetic annulenic ring currents for hexacyclic molecules. We have also studied the effect of substitution of benzene rings within the macrocycle. We find that as the number of benzene rings is increased the aromaticity increases for tetracyclic systems and decreases for hexacyclic systems. All the results have been analyzed with various microscopic parameters, including geometry, excitation gap, and NMR criteria.

Folding a Polymer via Two-Point Interaction with an External Folding Agent: Use of H-Bonding and Charge-Transfer Interactions

A polymer containing electron-rich aromatic donors (1,5-dialkoxynaphthalene (DAN)) was coerced into a folded state by an external folding agent that contained an electron-deficient aromatic acceptor (pyromellitic diimide (PM)) unit. The donor-containing polymer was designed to carry a tertiary amine moiety in the linking segment, which served as an H-bonding site for reinforcing the interaction with the acceptor containing folding agent that also bore a carboxylic acid group. The H-bonding interaction of the carboxylic acid and the tertiary amine brings the PDI unit between two adjacent DAN units along the polymer backbone to induce charge-transfer (C-T) interactions, and this in turn causes the polymer chain to form a pleated structure. Evidence for the formation of such a pleated structure was obtained from NMR titration studies and also by monitoring the C-T band in their UV-visible spectra. By varying the length of the segment that links the PDI acceptor to the carboxylic acid group, we showed that the most effective folding agent was the one that had a single carbon spacer, as evident from the highest value of the association constant. Control experiments with propionic acid clearly demonstrated the importance of the additional C-T interactions for venerating the folded structures. Further, solution viscosity measurements in the presence of varying amounts of the folding agent revealed a gradual stiffening of the chain in the case of the PDI carrying carboxylic acid, whereas no such affect was seen in the case of simple propionic acid. These observations were supported by D FT calculations of the interactions of a dimeric model of the polymer with the various folding agents; here too the stability of the complex was seen to be highest in the case of the single carbon spacer.