A multigrid method for predicting periodically fully developed flow

The use of multigrid methods in complex fluid flow problems is still under development. In this paper a full multigrid procedure has been incorporated in a finite volume solution for predicting fully developed fluid flow in a streamwise periodic geometry. Steady computations in two-dimensional body fitted co-ordinates have shown considerable savings in computation time by this multigrid method.     

Ultrafast proton-coupled electron-transfer dynamics in pyrene-modified pyrimidine nucleosides: model studies towards an understanding of reductive electron transport in DNA.

5-(Pyren-1-yl)-2'-deoxyuridine (PydU) and 5-(Pyren-1-yl)-2'-deoxycytidine (PydC) were used as model nucleosides for DNA-mediated reductive electron transport (ET) in steady-state fluorescence and femtosecond time-resolved transient absorption spectroscopy studies. Excitation of the pyrene moiety in PydU and PydC leads to an intramolecular electron transfer that yields the pyrenyl radical cation and the corresponding pyrimidine radical anion (dU.- and dC.-. By comparing the excited state dynamics of PydC and PydU, we derived information about the energy difference between the two pyrimidine radical anion states. To determine the influence of protonation on the rates of photoinduced intramolecular ET, the spectroscopic investigations were performed in acetonitrile, MeCN, and in water at different pH values. The results show a significant difference in the basicity of the generated pyrimidine radical anions and imply an involvement of proton transfer during electron hopping in DNA. Our studies revealed that the radical anion dC.- is being protonated even in basic aqueous solution on a picosecond time scale (or faster). These results suggest that protonation of dC.- may also occur in DNA. In contrast, efficient ET in PydU could only be observed at low pH values (< 5). In conclusion, we propose--based on the free energy differences and the different basicities--that only dT.- but not dC.- can participate as an intermediate charge carrier for excess electron migration in DNA.     

Study of the properties of the SHG with diode lasers

An experimental study of the second-harmonic generation (SHG) properties with nondiffraction-limited radiation is presented. This includes the dependency of the normalized conversion efficiency on the crystal length, the beam quality, and the focusing conditions. A Gauss–Schell-model-based theory of SHG is applied, which gives an improved simulation of the experimental results in comparison to the standard Boyd–Kleinman theory for nondiffraction-limited beams.     

Solvent effects on oxygen atom transfer reaction between manganese(V)-oxo corrole and alkene

Pseudo-first order reaction rate constants of 5,10,15-tris（pentafluorophenyl）corrole Mn（V）-oxo (F₁₅CMn（V）-oxo),5,15-bis（pentafluorophenyl）-10-（phenyl）corrole Mn（V）-oxo(F₁₀CMn（V）-oxo),5,15- bis（phenyl）-10-（pentafluorophenyl）corrole Mn（V）-oxo（F₅CMn（V）-oxo） and 5,10,15-tris（phenyl）corrole Mn（V）-oxo（F₀CMn（V）-oxo） with a series of alkene substrates in different solvents were determined by UV-vis spectroscopy.The results indicated that the oxygen atom transfer pathway between Mn（V）-oxo corrole and alkene is solvent-dependent.     

Aryl–Phenyl Scrambling in Intermediate Organopalladium Complexes: A Gas‐Phase Study of the Mizoroki–Heck Reaction

The intramolecular aryl–phenyl scrambling reaction within palladium–DPPP–aryl complex (DPPP=1,3‐bis(diphenylphosphino)propane) ions was analyzed by state‐of‐the‐art tandem MS, including gas‐phase ion/molecule reactions. The Mizoroki–Heck cross‐coupling reaction was performed in the gas phase, and the intrinsic reactivity of important intermediates could be examined. Moreover, linear free‐energy correlations were applied, and a mechanism for the scrambling reaction proceeding via phosphonium cations was assumed.     

Topography of antiferromagnetic domains using second harmonic generation with an external reference

2 O₃, in which the time-invariant second-harmonic reference can be generated either intrinsically by the crystal or externally by use of the new technique, so that both methods may be compared. The technique is then used to visualize the domain structure of YMnO₃, an antiferromagnetic crystal which does not provide the time-invariant reference wave intrinsically. The experiments demonstrate the wide applicability of the method. Received: 13 June 1997     

Ultrafast manipulation of antiferromagnetism of NiO

Photoexcitation of antiferromagnetic NiO leads to ultrafast reorientation of Ni2+ spins due to change of the magnetic anisotropy. Recovery of the magnetic ground state occurs as coherent oscillation of the antiferromagnetic order parameter between hard- and easy-axis states manifesting itself as quantum beating. The coherence time is approximately 1 ns with the beating frequency being determined by the anisotropy energy.     

Determination of the magnetic symmetry of hexagonal manganites by second harmonic generation

Optical second harmonic spectroscopy is introduced as a powerful supplement for the determination of complex magnetic structures. Experimental efforts are simplified and new degrees of freedom are opened. Thereby, some principal or technical restrictions of neutron or magnetic x-ray diffraction experiments are overcome. High spatial resolution leads to additional information about magnetically ordered matter. As an example, the noncollinear magnetic structure of the hexagonal manganites RMnO3 ( R = Sc, Y, Ho, Er, Tm, Yb, Lu) is analyzed. The results show that some earlier conclusions on their magnetic symmetry and properties should be revised.