Probe technique, nanosecond laser flash

Transient intermediates are most commonly observed by their absorption (transient absorption spectroscopy see ref. 185 for a compilation of absorption spectra of transient species). Various other methods for creating detectable amounts of reactive intermediates such as stopped flow, pulse radiolysis, temperature or pressure jump have been invented and novel, more informative, techniques for the detection and identification of reactive intermediates have been added, in particular EPR, IR and Raman spectroscopy (Section 3.8), mass spectrometry, electron microscopy and X-ray diffraction. The technique used for detection need not be fast, provided that the time of signal creation can be determined accurately (see Section 3.7.3). For example, the separation of ions in a mass spectrometer (time of flight) or electrons in an electron microscope may require microseconds or longer. Nevertheless, femtosecond time resolution has been achieved,186 187 because the ions or electrons are formed by a pulse of femtosecond duration (1 fs = 10 15 s). Several reports with recommended procedures for nanosecond flash photolysis,137,188-191 ultrafast electron diffraction and microscopy,192 crystallography193 and pump probe absorption spectroscopy194,195 are available and a general treatise on ultrafast intense laser chemistry is in preparation by IUPAC. 

The detection of short-lived transient species is often achieved by flash photolysis where an extremely short flash of UV/Vis radiation from a laser generates a high concentration of transient species, and a second probe beam monitors any changes that occur after the flash. Traditionally, UVA is spectroscopy has been used as a detection method. However, time-resolved infrared spectroscopy (TRIR), a combination of UV flash photolysis and fast IR detection, also has a long history. There are several different approaches to fast IR spectroscopy and the method of choice depends upon the timescale of the reaction. Measurements on the nanosecond to millisecond timescale are obtained using point-by-point techniques or by step-scan FTIR. In the point-by-point approach, a continuous wave IR laser (GO or diode) or globar is used as the IR source, which is tuned to one particular IR frequency (Figure 3). ... 

An intense short pulse of UV or visible radiation is used to electronically excite the sample, and the subsequent absorption changes are probed spectrophotomet-rically. The technique was first introduced by Norrish and Porter in 1949 [18] and at this time gas-filled discharge lamps were used, limiting the time resolution, which is principally governed by the duration of the excitation pulse, to microseconds. This is now usually termed conventional flash photolysis. However, with the development of laser pulsed techniques in place of flash excitation, the time resolution has been progressively reduced to subpicosecond, particularly with the use of mode-locked solid state lasers. Much current work utilises nanosecond time resolution with pulsed lasers such as ruby, neodymium and excimer lasers. 

Flash techniques were originally developed for the study of gas reactions [2,g] but were soon applied to solutions [2,h]. By the mid-60s, apparatus with a time-resolution of a few microseconds, using gas flash-lamps, had come into common use. With such equipment it was possible to identify transient species in solution from their spectra, and to determine their rates of decay and other processes. Excited states became recognised as distinct chemical species. The first study in which the spectra of the initial excited state, of the products and of some radical intermediates, were all detected in solution, and the kinetics investigated, was published in 1958 [2,k], Nanosecond pulses became available after the invention of the laser in 1960, but were not applied in flash photolysis until the problem of synchronising the analysing ( probe ) flash with the initiating ( pump ) flash was solved... 

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