Ultraviolet laser pulse spectroscopy

By using time-resolved RR spectroscopy with 400-nm laser excitation, the vibrational spectrum of the parent phenoxyl (produced pulse radiolytically in aqueous solution) was observed by Beck and Bras (32), and Tripathi and Schuler (18b). This classic spectrum is shown in Fig. 3. Tripathi (33) has reviewed the early literature. More recently, Spiro and co-workers (34) recorded ultraviolet (UV) RR spectra using 245-nm excitation of systematically isotopically labeled (13C6, and d, 170 isotopomers) phenolate and phenoxyl, and confirmed the assignments of vibrational modes by Tripathi and Schuler (18b). 

In principle, absorption spectroscopy techniques can be used to characterize radicals. The key issues are the sensitivity of the method, the concentrations of radicals that are produced, and the molar absorptivities of the radicals. High-energy electron beams in pulse radiolysis and ultraviolet-visible (UV-vis) light from lasers can produce relatively high radical concentrations in the 1-10 x 10 M range, and UV-vis spectroscopy is possible with sensitive photomultipliers. A compilation of absorption spectra for radicals contains many examples. Infrared (IR) spectroscopy can be used for select cases, such as carbonyl-containing radicals, but it is less useful than UV-vis spectroscopy. Time-resolved absorption spectroscopy is used for direct kinetic smdies. Dynamic ESR spectroscopy also can be employed for kinetic studies, and this was the most important kinetic method available for reactions... 

Experimental Techniques A absorption CIMS = chemical ionization mass spectroscopy CK = competitive kinetics DF discharge flow EPR = electron paramagnetic resonance FP = flash photolysis FT = flow tube FTIR Fourier transform intra-red GC = gas chromatography, UF = laser induced fluorescence LMR = laser magnetic resonance MS = mass spectroscopy PLP = pulsed laser photolysis SC = smog chamber SP = steady (continuous) photolysis UVF = ultraviolet flourescence spectroscopy... 

Most of the early gas lasers emitted in the visible region. Continuous-wave (CW) lasers such as Ar+ (351.1-514.5 nm), Kr+ (337.4-676.4 nm), and He-Ne (632.8 nm) are now commonly used for Raman spectroscopy. More recently, pulsed lasers such as Nd YAG, diode, and excimer lasers have been used for time-resolved and ultraviolet (UV) resonance Raman spectroscopy. 

Various forms of radiation have been used to produce ions in sufficient quantitites to yield neutral products for subsequent analysis. In principle, it should be possible to use intense beams of UV below ionization threshold for this purpose. To date, however, efforts to collect neutrals from resonant multiphoton ionization (REMPI) have not succeeded. In one experiment, 1 mbar of gaseous -propyl phenyl ether was irradiated at room temperature with a 0.1 W beam of 266 nm ultraviolet (from an 800 Hz laser that gives 8 n pulses) concurrent with a 0.5 W beam at 532 nm. The beams were intense enough not only to ionize the ether in the mass spectrometer, but also to excite it so that it expels propene. After several hours of irradiation < 10% of the starting material remained. Production of carbon monoxide and acetylene (decomposition products of the phenoxy group) could be detected by infrared absorption spectroscopy, but the yield of neutral propene (as measured by NMR spectroscopy) was infinitesimal. 

Pulse Laser Photolysis of Aqueous Ozone in the Microsecond Range Studied hy Time-Resolved Far-Ultraviolet Absorption Spectroscopy... 

Both methods therefore complement each other in high-resolution laser spectroscopy in the vacuum ultraviolet region, where single-photon spectroscopy is impeded by lack of tunable lasers. With intense light of a pulsed... 

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