orders are obtained employing the appropriate linear combination of Slater determinants for each C.I. eigenstate. The S, and S0 of dimethyl diene aliene 18 were also optimized using GAUSS1AN90 with an STO-3G basis set, and CASSCF with an active space of 4 was used for geometry optimization of S,.
The technical aspects of oil spill remote sensing are examined and the practical uses and drawbacks of each technology are given with a focus on unfolding technology. The use of visible techniques is ubiquitous, but limited to certain observational conditions and simple applications. Infrared cameras offer some potential as oil spill sensors but have several limitations. Both techniques, although limited in capability, are widely used because of their increasing economy. The laser fluorosensor uniquely detects oil on substrates that include shoreline, water, soil, plants, ice, and snow. New commercial units have come out in the last few years. Radar detects calm areas on water and thus oil on water, because oil will reduce capillary waves on a water surface given moderate winds. Radar provides a unique option for wide area surveillance, all day or night and rainy/cloudy weather. Satellite-carried radars with their frequent overpass and high spatial resolution make these day–night and all-weather sensors essential for delineating both large spills and monitoring ship and platform oil discharges. Most strategic oil spill mapping is now being carried out using radar. Slick thickness measurements have been sought for many years. The operative technique at this time is the passive microwave. New techniques for calibration and verification have made these instruments more reliable.
The technical aspects of oil spill remote sensing are examined and the practical uses and drawbacks of each technology are given with a focus on unfolding technology. The use of visible techniques is ubiquitous, but limited to certain observational conditions and simple applications. Infrared cameras offer some potential as oil spill sensors but have several limitations. Both techniques, although limited in capability, are widely used because of their increasing economy. The laser fluorosensor uniquely detects oil on substrates that include shoreline, water, soil, plants, ice, and snow. New commercial units have come out in the last few years. Radar detects calm areas on water and thus oil on water, because oil will reduce capillary waves on a water surface given moderate winds. Radar provides a unique option for wide area surveillance, all day or night and rainy/cloudy weather. Satellite-carried radars with their frequent overpass and high spatial resolution make these day-night and all-weather sensors essential for delineating both large spills and monitoring ship and platform oil discharges. Most strategic oil spill mapping is now being carried out using radar. Slick thickness measurements have been sought for many years. The operative technique at this time is the passive microwave. New techniques for calibration and verification have made these instruments more reliable.
A number of acyl radicals, RĊ=O, have been generated in hexane or di -t-butyl peroxide as solvent at room temperature by 308 nm laser flash photolysis, and their spectroscopic and kinetic properties have been examined by time-resolved infrared spectroscopy. The C=O stretching frequencies for the RĊ=O radicals are found to be higher than those of the corresponding aldehydes, RCHO, by between 108 and 128 cm-1, an effect attributed to a higher C=O bond order in the radicals. For the RĊ=O radicals some typical values of vC =O are: CH3Ċ=O, 1864 cm-1; (CH3)3CĊ=O, 1848 cm-1; and C6H5Ċ=O, 1828 cm-1, while the corresponding acylperoxyl radicals, RC(O)OO, formed by reaction with oxygen have vC =O values of 1838, 1840 and 1820 cm-1, respectively. The acyl radicals exhibit a reactivity towards a variety of substrates that is roughly comparable to that of simple alkyl radicals. For reactions of the benzoyl radical some typical rate constants/M-1 s-1 are: CCl4, 6.0x104; C6H5SH, 4.8×107; CCl3Br, 2.2×108; Tempo, 1.1×109; and oxygen, 1.8×109. Alkanoyl radicals have a rather similar reactivity to benzoyl. The propanoyl radical reacts with tributyltin deuteride with a rate constant of 3×105 M-1s-1. The hex-5-enoyl radical undergoes a 5-exo-trig cyclization to form the 2-oxocyclopentylmethyl radical with a rate constant of 2.2×105 s-1, a value which is almost identical to that for cyclization of the hex-5-enyl radical. It is hoped that our kinetic data will prove useful in the planning of organic synthetic strategies which involve acyl radical chemistry.
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