Advances in Photochemistry, Volume 18 by David H. Volman, George S. Hammond, Douglas C. Neckers

By David H. Volman, George S. Hammond, Douglas C. Neckers

A part of a continual sequence which explores the frontiers of photochemical study, this quantity includes reviews through specialists within the box who significantly examine latest facts.

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However, one of the disadvantages of FTIR spectroscopy for kinetic studies is that it is not possible to “sit” on a spectral feature and acquire temporally resolved data for a given number of laser shots. An entire interferogram must be scanned before any spectral information is obtained. To avoid prohibitively long data acquisition times, time-resolved measurements obtained by systematically varying the experimental parameters are usually limited to short scans and hence lower resolution. It must be stressed however that spectra at high resolution are first required to identify unambiguously the emitting species and to measure the degree of internal excitation.

E. HEARD doubtful, even with a larger mirror travel, that higher resolutions could be obtained with such a simple S S instrument because of the problem of keeping the mirror absolutely stationary during data acquisition over the entire scan. Rotational resolution of hydride molecules was readily demonstrated with this instrument, but individual rotational lines of CO and CO, could not be distinguished. The majority of studies observed IR emission from atomradical reactions in a discharge-flow system at a pressure of several Torr [38, 40, 82, 83).

01 cm s - l , below which the mirror moves too slowly to permit smooth scanning, and results in the He-Ne zero crossings generated at 316 Hz. When the photolysis excimer laser is triggered at this frequency, its output energy per shot decreases and shot to shot fluctuations increase compared with operation at lower repetition rates. Poorer data resulted at the end of runs requiring many interferograms to be co-added, which together with maintenance of mirror and window cleanliness, represents the most serious limitation of the technique as it stands.

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