Cooling spectroscopy

Meijer G, de Vries MS, Hunziker HE, Wendt HR (1990). Laser desorption jet-cooling spectroscopy of para-amino benzoic acid monomer, dimer, and clusters. J Chem Phys 92 7625-7635. 

Lai LK. Filseth SV. Sadowski CM. et al. 1990. Direct determination of benzo(a)pyrene and pyrene in solid environmental samples by jet-cooled spectroscopy. Int J Environ Anal Chem 40(1-4) 99-109. 

Meijer, G., de Vries, M.S., Hunziker, H.E., and Wendt, H.R., "Laser Desorption Jet-Cooling Spectroscopy of para-Amino Benzoic Acid Monomer, Dimer, and Clusters," Journal of Chemical Physics. 92 (12), 7625-7635,1990. 

The molecular constants that describe the stnicture of a molecule can be measured using many optical teclmiques described in section A3.5.1 as long as the resolution is sufficient to separate the rovibrational states [110. 111 and 112]. Absorption spectroscopy is difficult with ions in the gas phase, hence many ion species have been first studied by matrix isolation methods [113], in which the IR spectrum is observed for ions trapped witliin a frozen noble gas on a liquid-helium cooled surface. The measured frequencies may be shifted as much as 1 % from gas phase values because of the weak interaction witli the matrix. 

Optothemial spectroscopy is a bolonietric method that monitors the energy in a stream of molecules rather than in the light beam. A well collimated molecular beam is directed toward a liquid helium cooled bolometer. There will be energy... 

Fehrensen B, Hippier M and Quack M 1998 Isotopomer selective overtone spectroscopy by ionization detected IR + UV double resonance jet-cooled aniline Chem. Phys. Lett. 298 320-8... 

Boyarkine O V, Settle RDF and Rizzo T R 1995 Vibrational overtone spectra of jet-cooled CFgH by infrared laser assisted photofragment spectroscopy Ber. Bunsenges. Rhys. Chem. 99 504-13... 

Behm J M and Morse M D 1994 Spectroscopy of]et-cooled AIMn and trends in the electronic structure of the 3d transition metal aluminides J. Chem. Rhys. 101 6500... 

It was dissolved in 75 ml of pentane and the solution was cooled to about -30°C with swirling. Some oil precipitated NHR spectroscopy showed the presence of only a very small amount of the allene. The supernatant yellow liquid was decanted from the oil and, after some pentane had been removed by evacuation, the solution was cooled below -40°C. The pale yellow crystals (m.p. 52°C) were filtered off on a sintered-glass funnel (note 2). From the mother liquor an additional small amount of product was obtained, bringing the yield of NMR-pure material to 62%. 

IR spectroscopy is an inherently faster method than NMR and an IR spectrum is a superposition of the spectra of the various conformations rather than an average of them When 1 2 dichloroethane is cooled below its freezing point the crystalline matenal gives an IR spectrum consistent with a single species that has a center of symmetry At room temperature the IR spec trum of liquid 1 2 dichloroethane retains the peaks present in the solid but includes new peaks as well Explain these observations... 

Future Trends. Methods of laser cooling and trapping are emerging as of the mid-1990s that have potential new analytical uses. Many of the analytical laser spectroscopies discussed herein were first employed for precise physical measurements in basic research. AppHcations to analytical chemistry occurred as secondary developments from 10 to 15 years later. 

The intensely developing technique of high-resolution IR-spectroscopy of dimers composed of two different molecules in supersonic cooled jets offers a new promising approach to the quantum dynamics of reaction complexes. In essence, this is a unique possibility of modelling low-temperature chemical reactions. 

D. Frequencies Molecules vibrate (stretch, bend, twist) even if they are cooled to 0 K. This is the basis of infrared/Raman spectroscopy, where absorption of energy occurs when the frequency of molecular... 

Uracil, thymine, and cytosine have been studied using this technique (89JA2308 and references therein). For uracil and thymine, the dioxo tautomer predominates in the case of cytosine (70), three tautomers were detected, 70a, 70b, and 70c, the last one being the least abundant. The gas-phase tautomeric equilibrium of 2-pyridone 15a and 2-hydroxypyridine 15b has been studied by MW spectroscopy (93JPC46) using both a conventional spectrometer and a jet-cooled millimeter-wave spectrometer. The relative abundances are 3 1 in favor of the hydroxy form 15b, which exists in the Z conformation shown (Scheme 23). 

The ratio of the different isomeric products was found to vary with time, temperature, and initial concentration. This suggested that some kind of equilibration was occurring between isomers. I3C NMR spectroscopy of a reaction mixture showed, upon cooling, the reversible formation of a pair of signals in the anomeric region. These signals were ascribed to the anomeric carbon atoms of fructofuranosyl fluorides (10), which were presumed to be in equilibrium with the reactive fructofuranosyl cation, 11. 

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