Atomic in-plane disorder in Co/Pt superlattices

We have studied 111 and 001 oriented Co(3 Å)/Pt(18 Å) superlattices grown by molecular beam epitaxy via X-ray diffraction using synchrotron radiation. The diffraction peak shapes, for the scattering vector Q parallel to the film planes, were found to be characteristically different between these two films. For the 111 oriented sample, this broadening is characterized by a Lorentzian peak shape with a positional correlation length of the order of 50 Å. The data further indicate that the atomic correlation in the 111 sample has a long range orientational but only short range positional order.     

The effects of collisional quenching on degenerate four-wave mixing

We report a theoretical and experimental investigation of the effects of collisional quenching on resonant degenerate four-wave mixing (DFWM). Using single-mode laser radiation, peak signal intensity measurements were performed on an isolated line in the A – X transition of NO. By using appropriate mixtures of N₂ and CO₂ as buffer gases, we varied the collisional quenching rate over several orders of magnitude while maintaining a fixed total collisional dephasing rate. The mixtures had approximately 100 Torr total pressure and were at room temperature. For I/I _sat approximately equal to 0.02, DFWM intensities were found to be less affected by variations in quench rate than were laser-induced fluorescence (LIF) intensities (I and I _sat are the pump laser and one-photon saturation intensities, respectively). Moreover, for I/I _sat roughly equal to 0.5, DFWM intensities were observed to be nearly independent of quench rate. The results are compared to two theoretical predictions, with good agreement observed. Both theories indicate that the minimum sensitivity of DFWM to quenching occurs near I/I _sat1.     

Dynamics of a conformational change in aqueous 18-crown-6 by an ultrasonic absorption method

A temperature dependence study of the ultrasonic amplitudes, velocities, and relaxation times for a presumed conformational transition of noncomplexed aqueous 18-crown-6 (1,4,7,10,13,16-hexaoxacyclooctadecane) is discussed. At all temperatures a single relaxation was observed within a 15–255-MHz frequency range. The equilibrium constant for the presumed conformational transition \documentclass{article}\pagestyle{empty}\begin{document}$ {\rm CR}_1 \mathop \rightleftarrows\limits^{K_{12} } {\rm CR}_2 $\end{document} was determined to be K₂₁ = (2 ± 2) × 10^?2. The activation parameters are ΔH₂₁^≠ = 10.2 ± 1.0 kcal/mol, ΔS₂₁^≠ = 7.7 ± 0.2 cal/(mol·deg), ΔH₁₂^≠ = 7.4 ± 1.0 kcal/mol, and ΔS₁₂^≠ = 7.7 ± 0.2 cal/(mol·deg), while the thermodynamic enthalpy and entropy were found to be ?2.6 ± 1.0 kcal/mol and 0 ± 0.2 cal/(mol·deg), respectively. The rate constants at 25.0°C for the presumed conformational transition are k₂₁ = (1.0 ± 0.3) × 10⁷ sec^?1 and k₁₂ = (6.2 ± 0.2) × 10⁸ sec^?1.     

The steady-state approximation: Fact or fiction?

The kinetic equations for an 81-reaction model of a photochemical smog chamber have been solved using a complete numerical integration as well as a quasi-steady-state approximation (QSSA) procedure. The two sets of results differ markedly in their prediction of experimentally significant factors such as the hydrocarbon depletion rate and the ozone and (NO)_x peaking times. The sources of the discrepancy are traced to the fact that the assumed steady-state conditions were not satisfied, leading to errors in the concentrations of intermediate radicals which in turn affect critical rates in the reaction model. The occurrence of such discrepancies in various types of reaction models, and with different QSSA strategies, is discussed, and it is concluded that the extent of such errors in QSSA calculations cannot be reliably predicted. Their impact on conclusions regarding reaction mechanisms and rate constants can surpass uncertainties in experimental data; conversely the credibility of predictions derived through QSSA calculations becomes highly suspect. Since recently devloped methods for complete numerical integration of systems of kinetic equations are now available, it is recommended that these be adopted in future work, and that the use of QSSA be abandoned.     

Molecular orientation of a model liquid crystal alignment layer

An analytical methodology, involving the use of a combination of second harmonic generation (SHG) and linear dichroism, was utilized to probe the molecular orientation and angular distribution of a model liquid crystal (LC) alignment layer. In order to determine which film structure would be best suited for use as an alignment layer, the azo dye o-methyl red (MR) was covalently bound to a glass substrate using both monofunctional and trifunctional silane chemistry. The influence of solvent on the orientation and angular distribution of both thin films was also investigated. For the monofunctional silane film under water, the mean orientation angle of the MR molecular long axis was 67±4° and the width of an assumed Gaussian distribution was 32±2°. Under hexanes, the mean orientation angle was the same within error (63±1°) but the distribution width narrowed considerably to 22±1°. Molecular orientation within the trifunctional silane film exhibited little dependence on solvent. Under water, the mean orientation angle and angular distribution width were 76±3° and 30±1°, respectively. With hexanes as the solvent, the mean orientation angle and angular distribution width were 79±1° and 30±1°, respectively. Orientation insensitive SHG measurements indicated that surface coverage in the tri-functional silane film was twice that in the mono-functional silane film. The observed orientational differences were attributed to differences in the forces that dictate molecular orientation for the two systems. Based on the higher orientation angle, higher surface coverage and the lack of solvent dependence, MR-tri exhibits more desirable characteristics for use as an LC alignment layer.     

Optical properties of Yb-doped fibers and fiber lasers at high temperature

Recent advances in power scaling of Yb^+ 3-doped fiber lasers to the kilowatt level suggest a need to examine the performance of Yb^+ 3-doped silica at temperatures well above ambient. We report experimental results for the absorption coefficient, emission cross-section, fluorescence lifetime, and slope efficiency of a Yb³⁺-doped large mode area (LMA) silica fiber for temperatures spanning 23 °C-977 °C. To the best of our knowledge these are the highest temperatures to date for which these optical properties have been measured. We find a sharp reduction in the energy storing capability and lasing performance of Yb^+ 3:SiO₂ above 500 °C that coincides with the onset of non-radiative transitions in the excited state manifold (thermal quenching). As the temperature increases from room temperature to 977 °C, absorption in the 1020-1120 nm operating band increases monotonically, concurrent with a reduction in absorption at the 920-nm and 977-nm pumping bands. Conversely, the spectral weight of the emission cross-section shifts from transitions above 1010 nm to those below, with the exception of the 977-nm emission band.