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 learn, this quantity includes reviews by way of specialists within the box who significantly learn present info.

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4 mTorr, total pressure 4 Torr, 3 p s time resolution. (a) Data were taken over 200 laser shots at 68 J cm-'. (b)Data for 100 laser shots at 59 J cm-'. Note the different timescales for the two sets of traces. Reproduced with permission from Ref. 82. 52 G . HANCOCK AND D. E. HEARD evolution of 50 excitation cycles was recorded and averaged for each interferometric mirror position (or between adjacent sampling positions for a quasi-SS scan). The strongest emission was from NO(u’ = 1-10), generated from the reactions of N(,D) and N(,P) with 0,.

Reproduced with permission from Ref. 45. TIME-RESOLVED FTIR EMISSION STUDIES 39 performed elsewhere [115] show that [OH(u’ = O)]/[OH(u’ = l)] is greater than 1, and hence the overall vibration distribution is bimodal, suggesting the existence of two dynamically different reaction channels. The PES permits both a direct H atom abstraction, predominantly populating O H (0’> l), and an insertion (forming a long-lived HSOH or H,SO intermediate) which populates O H (u‘ c 1). The S S implementation of time-resolved FITR spectroscopy has been used to measure the initial vibrational distributions of a number of reactions [37].

The detection time of 4-6 p s required pressures of below 10 mTorr in order to observe products before collisions. 25 cm-’ scans were recorded at higher pressures). Rotational levels as high as J = 50 were detected in several vibrational states of CO. The vibrational distribution of the C O fragment was closely approximated by a temperature of 2000 K, whereas that of the rotational excitation was higher at 3350 K. Both were successfully modelled by a “pure impulsive” mechanism for the fragmentation of an initial bent acetyl fragment.

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