Nanoscale polyoxometalate‐based inorganic/organic hybrids

The latest advances in the area of polyoxometalate (POM)‐based inorganic/organic hybrid materials prepared by self‐assembly, covalent modification, and supramolecular interactions are presented. This Review is composed of five sections and documents the effect of organic cations on the formation of novel POMs, surfactant encapsulated POM‐based hybrids, polymeric POM/organic hybrid materials, POMs‐containing ionic crystals, and covalently functionalized POMs. In addition to their role in the charge‐balancing, of anionic POMs, the crucial role of organic cations in the formation and functionalization of POM‐based hybrid materials is discussed. DOI 10.1002/tcr.201100002     

The design of a new concept chromatography column

Active Flow Management is a new separation technique whereby the flow of mobile phase and the injection of sample are introduced to the column in a manner that allows migration according to the principles of the infinite diameter column. A segmented flow outlet fitting allows for the separation of solvent or solute that elutes along the central radial section of the column from that of the sample or solvent that elutes along the wall region of the column. Separation efficiency on the analytical scale is increased by 25% with an increase in sensitivity by as much as 52% compared to conventional separations.     

Conformer specific dissociation dynamics of iodocyclohexane studied by velocity map imaging

The photodissociation dynamics of iodocyclohexane has been studied using velocity map imaging following excitation at many wavelengths within its A-band (230 ≤ λ ≤ 305 nm). This molecule exists in two conformations (axial and equatorial), and one aim of the present experiment was to explore the extent to which conformer-specific fragmentation dynamics could be distinguished. Ground (I) and spin-orbit excited (I?) state iodine atom products were monitored by 2 + 1 resonance enhanced multiphoton ionization, and total kinetic energy release (TKER) spectra and angular distributions derived from analysis of images recorded at all wavelengths studied. TKER spectra obtained at the longer excitation wavelengths show two distinct components, which can be attributed to the two conformers and the different ways in which these partition the excess energy upon C-I bond fission. Companion calculations based on a simple impulsive model suggest that dissociation of the equatorial (axial) conformer preferentially yields vibrationally (rotationally) excited cyclohexyl co-fragments. Both I and I? products are detected at the longest parent absorption wavelength (λ ～ 305 nm), and both sets of products show recoil anisotropy parameters, β > 1, implying prompt dissociation following excitation via a transition whose dipole moment is aligned parallel to the C-I bond. The quantum yield for forming I? products, Φ(I?), has been determined by time resolved infrared diode laser absorption methods to be 0.14 ± 0.02 (at λ = 248 nm) and 0.22 ± 0.05 (at λ = 266 nm). Electronic structure calculations indicate that the bulk of the A-band absorption is associated with transition to the 4A(') state, and that the (majority) I atom products arise via non-adiabatic transfer from the 4A(') potential energy surface (PES) via conical intersection(s) with one or more PESs correlating with ground state products.     

Improved Lower Bounds for the Critical Probability of Oriented Bond Percolation in Two Dimensions

We present a coupled decreasing sequence of random walks on Z that dominate the edge process of oriented bond percolation in two dimensions. Using the concept of random walk in a strip, we describe an algorithm that generates an increasing sequence of lower bounds that converges to the critical probability of oriented percolation p_c. From the 7th term on, these lower bounds improve upon 0.6298, the best rigorous lower bound at present, establishing 0.63328 as a rigorous lower bound for p_c. Finally, a Monte Carlo simulation technique is presented; the use thereof establishes 0.64450 as a non-rigorous five-digit-precision (lower) estimate for p_c. Mathematics Subject Classification (1991): 60K35 Supported by CNPq (grant N.301637/91-1). Supported by a grant from CNPq.     

Extension of the N-point Padé approximants solution of the Eliashberg equations to T ∼ Tc

Vidberg and Serene introduced a very useful technique for calculating the low temperature (T « T_c) gap function of a superconductor which bypasses the real-frequency singular integral equations of Eliashberg. Blashke and Blocksdorf recognized and resolved a difficulty with the technique thereby extending it to higher temperatures. We present a much simpler method of doing essentially the same thing and, for a strong-coupling superconductor at a temperature near T_c, compare the gap functions calculated using these methods with the accurate one computed directly from the real-frequency equations.     

Time-resolved electron spin resonance with electron spin polarization (CIDEP) as a sensitive probe of degenerate electron exchange reactions

It is shown that the occurrence of electron-exchange processes produces a distinctive effect in the time-resolved electron spin resonance spectra of spin-polarized radicals observed in the continuous presence of a microwave field. The effects observed are consistent with a theory based upon the Bloch equations.     

Applications of ESCA to polymer chemistry. IV. The composition and structure of copolymers of ethylene with tetrafluoroethylene

Molecular core binding energies have been measured by ESCA for a series of copolymers of tetrafluoroethylene and ethylene. Detailed analysis of the results demonstrates the utility of ESCA for determination of copolymer compositions and for providing information on important structural features for these copolymers.     

REMPI-TOF studies of the translational anisotropy and the polarization of the O ((1)D2) photofragment angular momentum following ozone photolysis at 298 nm

The translational anisotropy and the polarization of the electronic angular momentum of the O ((1)D2) fragment produced from the 298 nm photodissociation of ozone have been determined using resonance enhanced multiphoton ionization (REMPI) in conjunction with time-of-flight mass spectrometry (TOFMS). The translational anisotropy parameter beta, which is necessarily averaged over the O2 co-fragment rotational distribution, is measured to be 1.08 +/- 0.04. This is consistent with that expected for the (1)B2 <-- (1)A1 transition within an impulsive model if the tangential velocity associated with the zero point motion of the bend is constricted to opening the bond angle. Molecular frame polarization parameters of rank up to k = 4 have been extracted for the O ((1)D2) fragment and the calculated m(J) populations show a strong preference for the absolute value(m(J)) = 1 states. A small coherence term is also observed, a manifestation of the nuclear geometry of the dissociating molecule and the existence of possible non-adiabatic processes in the exit channel. The orientation associated with the mapping of the photon helicity onto the O ((1)D2) electronic angular momentum distribution was observed to have been quenched. However, the parameter gamma1', which describes the contribution to the orientation from a coherent superposition of a parallel and perpendicular excitation where the photofragment angular momentum lies perpendicular to both the recoil velocity and to the transition dipole moment, was determined to be -0.06.