Electron spin resonance studies atmospheres

It is likely that the answers to these questions will come only from more selective and sophisticated experiments than have been done hitherto, although some useful directions have been established. The use of high-sensitivity electron spin resonance for the study in situ of anticipated radical species will likely be possible, if the background signals from other radiation-produced species are not too intense. Studies of the chemistry of implanted atoms and ions in solid organometallic substrates will make it possible to start with totally unbound atoms which suffer no Auger ionization and thus to simulate the extreme of the total recoil. Careful studies of the thermal annealing effects, especially in the presence of reactive atmospheres, will... 

The problem of bringing a large magnet into the field for ambient measurements has been overcome in electron paramagnetic resonance (EPR, also called electron spin resonance, ESR) by Mihelcic, Helten, and coworkers (93-99). They combined EPR with a matrix isolation technique to allow the sampling and radical quantification to occur in separate steps. The matrix isolation is also required in this case because EPR is not sensitive enough to measure peroxy radicals directly in the atmosphere. EPR spectroscopy has also been used in laboratory studies of peroxy radical reactions (100, 101). 

In very pure nonpolar dielectric liquids, electron injection currents at very sharp tips follow the Fowler-Nordheim voltage dependence (Halpem and Gomer, 1969), just as is the case in solid insulators, and in a gas, as described before. In a study of the electrochemical behavior of CNT cathodes (Krivenko et al., 2007) direct experimental proof was found of electron emission into the liquid hexamethylphosphortriamide, which was chosen because it is a convenient solvent for the visualization of solvated electrons at room temperature the solution will show an intense blue coloration upon the presence of solvated electrons. Electron spin resonance showed prove of a free electron. Electrogenerated (as opposed to photogenerated) solvated electrons have been used in the synthesis of L-histidinol (Beltra et al., 2005), albeit that in that work the electrons were generated electrochemically from a solution of LiCl in EtNH2, which is a solvent that is easier to handle than liquid ammonia (boiling points at atmospheric pressure are 17 °C and -33.34 °C, respectively). 

Metal- and proton-exchanged zeolites have been recently attracted much attention because of their selective catalytic activity to efficiently reduce nitrogen monoxide (NO) by hydrocarbon in an 02-rich atmosphere [1]. The formation of nitrogen dioxide (NO2) from NO and O2 has been suggested as an important step in the selective reduction [2, 3] NO2 is one of rare stable paramagnetic gaseous molecules and has been subjected to electron spin resonance (ESR) studies [4-7]. The ESR parameters and their relation/to the electronic structure have been well established [4] and NO2 can be used as a "spin probe" for the study of molecular dynamics at the gas-solid interface by ESR. 

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