An investigation of the chemical and physical properties of pristine, electrochromically damaged, and photochromically damaged KTiOPO{sub 4} (KTP) using surface analytical and optical spectroscopic techniques

A variety of experimental techniques were employed to study the properties of electrochromically (EC) damaged, photochromically (PC) damaged, and pristine KTiOP0{sub 4} (KTP). Additionally, nonlinear optical calculations were performed to complement the experimental work in an effort to elucidate the respective mechanisms operative in producing EC and PC damage to KTP. Several independent experiments indicate that there is Ti deficiency in the EC damaged material, which is due to migration of these ions to the electrode surface. The laser experiments indicate that UV radiation can produce reversible PC damage. UV-producing SFG processes accidentally occurring in SHG cut KTP may lead to macroscopic damage. It must be emphasized that a fundamentally different mechanism is responsible for EC damaged versus PC damaged KTP

A Broadly Applicable Strategy for Entry into Homogeneous Nickel(0) Catalysts from Air-Stable Nickel(II) Complexes

A series of air-stable nickel complexes of the form L[subscript 2]Ni(aryl) X (L = monodentate phosphine, X = Cl, Br) and LNi(aryl)X (L = bis-phosphine) have been synthesized and are presented as a library of precatalysts suitable for a wide variety of nickel-catalyzed transformations. These complexes are easily synthesized from low-cost NiCl[subscript 2]·6H[subscript 2]O or NiBr[subscript 2]·3H[subscript 2]O and the desired ligand followed by addition of 1 equiv of Grignard reagent. A selection of these complexes were characterized by single-crystal X-ray diffraction, and an analysis of their structural features is provided. A case study of their use as precatalysts for the nickel-catalyzed carbonyl-ene reaction is presented, showing superior reactivity in comparison to reactions using Ni(cod)[subscript 2]. Furthermore, as the precatalysts are all stable to air, no glovebox or inert-atmosphere techniques are required to make use of these complexes for nickel-catalyzed reactions.National Institute of General Medical Sciences (U.S.) (GM63755)National Science Foundation (U.S.). Graduate Research Fellowshi

Use of multivariate regression for analysis of CO{sub 2} laser lidar data from long pathlengths in ambient atmosphere

Until recently use of lasers for long path absorption measurements has relied on using differential absorption at two wavelengths to look for one species at a time in the atmosphere. With the advent of multi-line CO{sub 2} lasers it is now feasible to generate 30 to 40 lines in a rapid burst to look for spectra of all the chemical species that may be present. Measurements have been made under relatively constant meteorological conditions in a summertime desert environment with a multi-line tunable laser. Multivariate regression analysis of this data shows that the spectra can be accurately fit using a small number of spectral factors or eigenvectors of the time dependent spectral data matrix. The factors can be rationalized in terms of lidar system effects and atmospheric composition changes

The Addition of a Second Lanthanide Ion to Increase the Luminescence of Europium(III) Macrocyclic Complexes

At present, the microscopic visualization of luminescent labels containing lanthanide(III) ions, primarily europium(III), as light-emitting centers is best performed with time-gated instrumentation, which by virtually eliminating the background fluorescence results in an improved signal to noise ratio. However, the use of the europium(III) macrocycle, Quantum Dye{trademark}, in conjunction with the strong luminescence enhancing effect (cofluorescence) of yttrium(III) or gadolinium(III), can eliminate the need for such specialized instrumentation. In the presence of Gd(III), the luminescence of the Eu(III)-macrocycles can be conveniently observed with conventional fluorescence instrumentation at previously unattainable low levels. The Eu(III) {sup 5}D{sub 0} {r_arrow} {sup 7}F{sub 2} emission of the Eu(III)-macrocycles was observed as an extremely sharp band with a maximum at 619 nm and a clearly resolved characteristic pattern. At very low Eu(III)-macrocycle concentrations, another sharp emission was detected at 614 nm, arising from traces of Eu(III) present in even the purest commercially available gadolinium products. Discrimination of the resolved emissions of the Eu(III)-macrocycle and Eu(III) contaminant should provide a means to further lower the limit of detection of the Eu(III)-macrocycle

Atmospheric effects on CO{sub 2} differential absorption lidar performance

CO{sub 2} differential absorption lidar (DIAL) performance can be adversely affected by the ambient atmosphere between the laser transmitter and the target through a number of different processes. This work addresses two sources of atmospheric interference with multispectral CO{sub 2} DIAL measurements: effects due to beam propagation through atmospheric turbulence and extinction due to absorption by atmospheric gases. The authors compare measurements of the effective beam size after propagation to predictions from a beam propagation model that includes turbulence effects such as beam steering and beam spreading. They also compare the experimental measurements of atmospheric extinction to those predicted by both a standard atmospheric transmission model (FASCODE) and a chemometric analysis