Synthesis and studies of a trinuclear Mn(II) carboxylate complex

We report a carboxylate triangle consisting of three manganese(II) centres which is made from manganese(II) carbonate and pivalic acid. The magnetic exchange within the triangle is extremely weak, and antiferromagnetic. Several models have been used to fit the magnetic data, and the best fit uses two weak antiferromagnetic coupling constants of J(1)=-0.588 cm(-1) and J(2)=-0.855 cm(-1). Exchange interactions between the metal centres has been calculated using DFT adopting all the three possible Heisenberg models for a trinuclear system and the results are compared with experimental values. Spin density distribution is used to analyse the nature of the coupling between the metal centres. EPR spectroscopy has been used to explore the nature of the ground state. Recrystallisation of the trinuclear compound from MeCN gives a polymer, while oxidation in air leads to a known compound--an edge-sharing bitetrahedral (MnIII2MnII4) cage.     

On a Question of Haskell P. Rosenthal Concerning a Characterization of c0 and lp

The following property of a normalized basis in a Banach spaceis considered: any normalized block sequence of the basis hasa subsequence equivalent to the basis. Under uniformity or othernatural assumptions, a basis with this property is equivalentto the unit vector basis of c₀ or l_p. An analogous problem concerningspreading models is also addressed. 2000 Mathematics SubjectClassification 46B20 (primary), 46B15 (secondary).     

Construction of Pseudorandom Binary Sequences Using Additive Characters

In earlier papers the authors studied finite pseudorandom binary sequences, and they constructed sequences with strong pseudorandom properties. In these earlier constructions multiplicative characters were used. In this paper a new construction is presented which utilizes properties of additive characters. These new sequences can be computed fast, they are well-distributed relative to arithmetic progressions and their correlations of small order are small, but the price paid for the fast computation is that the correlations of large order can be large.     

F-18-FDG uptake is a reliable predictory of functional recovery of akinetic but viable infarct regions as defined by magnetic resonance imaging before and after revascularization

Identification of akinetic but viable myocardium is important for the selection of patients for coronary revascularization. In order to assess predictive values of end-diastolic wall thickness and dobutamine induced wall thickening obtained by magnetic resonance imaging (MRI) and [18F]Fluorodeoxyglucose uptake assessed by positron emission tomography (F-18-FDG-PET), these parameters were compared to recovery of left ventricular function after successful revascularization. Forty patients with chronic myocardial infarction and regional a- or dyskinesia by ventriculography underwent rest- and dobutamine-MRI studies (10 microg dobutamine/kg body weight/min) and F-18-FDG-PET. Viability of the infarct region was considered to be present if; 1) end-diastolic wall thickness was > or =5.5 mm; 2) dobutamine induced wall thickening > or =2 mm could be measured; and 3) normalized F-18-FDG-uptake was > or =50% in > or =50% of akinetic segments. Preserved end-diastolic wall thickness was found in 32/40 patients, functional improvement during dobutamine infusion in 26/40 patients and preserved F-18-FDG-uptake in 29/40 patients. After revascularization regional left ventricular function improved in 25/40 patients. Positive and negative predictive values and diagnostic accuracy were 78%, 100%, and 83% for preserved end-diastolic wall thickness, 92%, 93%, and 93% for dobutamine inducible contraction reserve and 86%, 100%, and 90% for preserved F-18-FDG-uptake. Quantitative assessment of dobutamine induced systolic wall thickening by MRI and F-18-FDG-uptake by PET are highly accurate techniques for the identification of viable myocardium and prediction of functional recovery after successful revascularization. Preserved end-diastolic wall thickness results in an overestimation of viable myocardium compared to functional improvement, but wall thickness <5.5 mm excludes recovery of regional function.     

Frictional dynamics of fluorine-terminated alkanethiol self-assembled monolayers

The frictional dynamics of fluorine-terminated alkanethiol (S(CH2)8CF3) self-assembled monolayers (SAMs) on gold are studied using molecular dynamics simulations. The simulations treat the interactions between two SAMs on flat surfaces. The structure and frictional behavior are investigated as a function of applied pressure (200 MPa to 1 GPa) for a shear velocity of 2 m/s and compared to methyl-terminated alkanethiol SAMs. The maximum adhesive pressure between the SAMs is 220 MPa for both end groups. In agreement with experiments on the molecular scale, the shear stress and the coefficient of friction for CF3-terminated alkanethiols are larger than for CH3-terminated alkanethiols. The main source for the difference is primarily the tighter packing of the fluorinated terminal group resulting in a higher degree of order. The molecular scale coefficient of friction is correlated with the degree of order among all the systems.     

The "JK-only" approximation in density matrix functional and wave function theory

Various energy functionals applying the "JK-only" approximation which leads to two-index two-electron integrals instead of four-index two-electron integrals in the electron-electron interaction term of the electronic energy are presented. Numerical results of multiconfiguration self-consistent field calculations for the best possible "JK-only" wave function are compared to those obtained from the pair excitation multiconfiguration self-consistent (PEMCSCF) method and two versions of density matrix functional theory. One of these is derived making explicit use of some necessary conditions for N representability of the second-order density matrix. It is shown that this method models the energy functional based on the best possible "JK-only" wave function with good accuracy. The calculations also indicate that only a minor fraction of the total correlation energy is incorporated by "JK-only" approaches for larger molecules.     

Observing photochemical transients by ultrafast x-ray absorption spectroscopy

Accurate determination of the transient electronic structures, which drive photochemical reactions, is crucial in chemistry and biology. We report the detection of transient chemical changes on the picosecond time scale by x-ray-absorption near-edge structure of photoexcited aqueous [Ru(bpy)(3)](2+). Upon ultrashort laser pulse excitation a charge transfer excited state having a 300 ns lifetime is formed. We detect the change of oxidation state of the central Ru atom at its L3 and L2 edges, at a temporal resolution of 100 ps with the zero of time unambiguously determined.     

High-frequency volume and boundary acoustic backscatter fluctuations in shallow water

Volume and boundary acoustic backscatter envelope fluctuations are characterized from data collected by the Toroidal Volume Search Sonar (TVSS), a 68 kHz cylindrical array capable of 360 degrees multibeam imaging in the vertical plane perpendicular to its axis. The data are processed to form acoustic backscatter images of the seafloor, sea surface, and horizontal and vertical planes in the volume, which are used to attribute nonhomogeneous spatial distributions of zooplankton, fish, bubbles and bubble clouds, and multiple boundary interactions to the observed backscatter amplitude statistics. Three component Rayleigh mixture probability distribution functions (PDFs) provided the best fit to the empirical distribution functions of seafloor acoustic backscatter. Sea surface and near-surface volume acoustic backscatter PDFs are better described by Rayleigh mixture or log-normal distributions, with the high density portion of the distributions arising from boundary reverberation, and the tails arising from nonhomogeneously distributed scatterers such as bubbles, fish, and zooplankton. PDF fits to the volume and near-surface acoustic backscatter data are poor compared to PDF fits to the boundary backscatter, suggesting that these data may be better described by mixture distributions with component densities from different parametric families. For active sonar target detection, the results demonstrate that threshold detectors which assume Rayleigh distributed envelope fluctuations will experience significantly higher false alarm rates in shallow water environments which are influenced by near-surface microbubbles, aggregations of zooplankton and fish, and boundary reverberation.     

Equatorial Plane Circular Orbits in the Taub-NUT Spacetime

Accelerated circular orbits in the equatorial plane of the Taub-NUT spacetime are analyzed to investigate the effects of its gravitomagnetic monopole source. The effect of a small gravitomagnetic monopole on these orbits is compared to the corresponding orbits pushed slightly off the equatorial plane in the absence of the monopole.     

Overcomplete Free Energy Functional for D = 1 Particle Systems with Next Neighbor Interactions

We deduce an overcomplete free energy functional for D=1 particle systems with next neighbor interactions, where the set of redundant variables are the local block densities _i of i interacting particles. The idea is to analyze the decomposition of a given pure system into blocks of i interacting particles by means of a mapping onto a hard rod mixture. This mapping uses the local activity of component i of the mixture to control the local association of i particles of the pure system. Thus it identifies the local particle density of component i of the mixture with the local block density _i of the given system. Consequently, our overcomplete free energy functional takes on the hard rod mixture form with the set of block densities _i representing the sequence of partition functions of the local aggregates of particle numbers i. The system of equations for the local particle density of the original system is closed via a subsidiary condition for the block densities in terms of . Analoguous to the uniform isothermal-isobaric technique, all our results are expressible in terms of effective pressures. We illustrate the theory with two standard examples, the adhesive interaction and the square-well potential. For the uniform case, our proof of such an overcomplete format is based on the exponential boundedness of the number of partitions of a positive integer (Hardy-Ramanujan formula) and on Varadhan's theorem on the asymptotics of a class of integrals.