Chemical reaction fronts in ordered and disordered cellular flows with opposing winds

We present experiments on the motion of chemical fronts in ordered and disordered vortex flows with imposed uniform winds. Fronts in a chain of alternating vortices are found to freeze (pin to the separatrix) for a wide range of opposing winds that grows nonlinearly with the characteristic strength of the underlying vorticity. Experiments in spatially disordered flows demonstrate that freezing of fronts is common to cellular flows; furthermore, it is not dependent on boundary conditions. We therefore anticipate similar pinning in a wide range of 2D cellular flows and front-producing systems.     

Temperature dependence of photoluminescence in amorphous Si1-xCx:H films

We have investigated the temperature dependence of photoluminescence in hydrogenated amorphous silicon-carbon alloys a-Si_1-xC_x:H prepared by glow discharge in the low-power regime. The radiative recombination process, due to photocarriers trapped on band-edge states, is in competition with the thermal escape of the photocarriers into the mobility bands. The model gives a quantitative fit with experiment, without any adjustable parameter, provided the width of the band-edge distribution of states is taken as the width of the conduction band only (measured by “photo-induced infra-red spectroscopy”) and not as the Urbach energy, as it is usually assumed.     

Theories in polymer science - helpful or inhibiting?

Theories in polymer science play an important role in how experiments are designed and results interpreted. Three areas of polymer chemistry are focussed on: step growth polymerization, particularly predictions of equal reactivity of functional groups; free radical chain polymerization with emphasis on structural irregularities and the consequences of these structures for previous theories; free radical copolymerization and the many models at present under discussion aimed at providing a theoretical basis for predicting the outcome of such copolymerization. The question of whether or not we as polymer chemists have been helped or hindered by theory is addressed.     

Copper(II) complexes of 2-amino-5-chloro-3-fluoropyridine: syntheses and magnetic properties of (3,5-FCAP)2CuX2 and (3,5-FCAPH)2CuX4

Using 2-amino-5-chloro-3-fluoropyridine, two new copper halide coordination complexes and two new salts have been synthesized: [(3,5-FCAP)₂CuCl₂] (1), [(3,5-FCAP)₂CuBr₂](2), (3,5-FCAPH)₂[CuCl₄] (3) and (3,5-FCAPH)₂[CuBr₄] (4) [3,5-FCAP?=?2-amino-5-chloro-3-fluoropyridine; 3,5-FCAPH?=?2-amino-5-chloro-3-fluoropyridinium]. These complexes have been analyzed through single-crystal X-ray diffraction and temperature-dependent magnetic susceptibility. Compounds 1 and 2 crystallize in the triclinic space group P-1, while 3 and 4 crystallize in the monoclinic space group P2₁/c. All structures were distinct, with 1 giving a bihalide bridged chain, 2 yielding a halide bridged dimer, 3 forming a two-halide bridged chain via short Cl???Cl contacts, and 4 producing a rectangular sheet via short Br???Br contacts. All four compounds exhibit anti-ferromagnetic interactions and were fit to linear chain (1 and 3), dimer (2), and rectangular 2-D sheet (4) models. The resulting J/k_B values are ?3.4(1), ?31.3(8), ?0.9(1), and ?9.46(6)?K with an α value (α?=?J?/J) of 0.06(2), respectively.     

X-ray absorption spectroscopy and density functional theory studies of [(H3buea)FeIII-X]n- (X = S2-, O2-, OH-): comparison of bonding and hydrogen bonding in oxo and sulfido complexes

Iron L-edge, iron K-edge, and sulfur K-edge X-ray absorption spectroscopy was performed on a series of compounds [Fe(III)H(3)buea(X)](n-) (X = S(2-), O(2-), OH(-)). The experimentally determined electronic structures were used to correlate to density functional theory calculations. Calculations supported by the data were then used to compare the metal-ligand bonding and to evaluate the effects of H-bonding in Fe(III)(-)O vs Fe(III)(-)S complexes. It was found that the Fe(III)(-)O bond, while less covalent, is stronger than the Fe(III)(-)S bond. This dominantly reflects the larger ionic contribution to the Fe(III)(-)O bond. The H-bonding energy (for three H-bonds) was estimated to be -25 kcal/mol for the oxo as compared to -12 kcal/mol for the sulfide ligand. This difference is attributed to the larger charge density on the oxo ligand resulting from the lower covalency of the Fe-O bond. These results were extended to consider an Fe(IV)(-)O complex with the same ligand environment. It was found that hydrogen bonding to Fe(IV)(-)O is less energetically favorable than that to Fe(III)(-)O, which reflects the highly covalent nature of the Fe(IV)(-)O bond.     

Normal Ordering and Abnormal Nonsense

The technique of the normal ordering of non-commuting operators is an important tool in the solution of problems involving creation and annihilation operators in quantum physics, such as in many-body theory or quantum optics. We point out the inconsistencies in previous definitions of the two standard normal ordering procedures for such operators, and show how consistent definitions may be made.