Nanosecond Flash Photolysis Measurements

Nanosecond Flash Photolysis Measurements.—A computer-controlled ns flash photolysis spectrometer has been described. The system was employed in a study of the photochemistry of xanthene dyes in solution. A nitrogen laser was used to provide 2—3 mJ excitation pulses at 337.1 nm for a ns flash photolysis study of electron-transfer reactions of phenolate ions with aromatic carbonyl triplets. A PDP II computer was used to control the transient digitizer employed for detection, and to subsequently process the data. A nanosecond transient absorption spectrophotometer has been constructed using a tunable dye laser in a pulse-probe conflguration with up to 100 ns probe delayA method for reconstructing the time-resolved transient absorption was discussed and results presented for anthracene in acetonitrile solution. The time-resolution of ns flash photolysis may be greatly increased by consideration of the integral under the transient absorption spectrum. Decay times comparable to or shorter than the excitation flash may be determined by this method. 

Many varied laser systems have been used for ns-flash photolysis experiments. For example, the kinetics of the electron-transfer quenching of triplet methylene 

Other applications of laser flash photolysis have included (a) a study of the bimolecular rate constant for the reaction between singlet oxygen and several lipid-soluble substances,(b) an investigation of quenching, solvent, and temperature effects on the photolysis of indoles, (c) the time dependence of the quenching of aromatic hydrocarbons by tetramethylpiperidine TV-oxide, and d) the kinetics of the geminate recombination of aromatic free radicals. Finally, flash photolysis has been utilized in order to examine the feasibility of a tunable IF laser (479—498 nm) and an ICl laser (430 nm).  

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Lewis J W, Yee G G and Kliger D S 1987 Implementation of an optical multichannel analyzer controller for nanosecond flash photolysis measurements Rev. Sol. Instrum. 58 939-44... 

Recent studies by Schuster and collaborators67,54, based on nanosecond laser flash techniques, revealed important conclusions, including (a). The enone excited state responsible for the photocycloaddition is the jt-Tt which possesses different polarization than the n-7T state, considered in rationalizing the effect of the oriented jr-complex. (b) Direct measurement of the reactivity scale of alkenes measured by nanosecond flash photolysis provided different results from those obtained with no consideration of the diradical fragmentation to starting materials. 

All systems were probed in steady-state fluorescence, absorption and time resolved emission lifetime studies at room temperature. Additionally, time resolved femtosecond transient absorption and nanosecond laser flash photolysis measurements were carried out. 

As has been shown by time-resolved flash photolysis measurements in colloidal titanium dioxide suspensions trapping is a very fast process. Rothenberger et al. performed picosecond and nanosecond transient absorption experiments on titanium dioxide and observed that the electron trapping time was faster than 30 ps, the time resolution of their laser system [4e]. The trapping time for holes was estimated to be < 250 ns. In a recent picosecond study by Serpone et al. on titanium dioxide colloids solutions of varying diameters it was observed that the spectra of trapped electrons as well as of trapped holes are fully developed after a laser... 

Fermi golden rule, 268 Filipescu, N., 291 Fisch, M. H., 307 Fischer, F., 379 Flash photolysis, 80-92 of aromatic hydrocarbons, 89, 90 determination of jsc, 228-230 determination of triplet lifetime, 240-242 energy of higher triplet levels, 219-220 flash kinetic spectrophotometry, 82, 83 measurement of triplet spectra, 81,82 nanosecond flash kinetic apparatus, 89 nanosecond flash spectrographic apparatus, 88... 

Laser flash photolysis experiments48,51 are based on the formation of an excited state by a laser pulse. Time resolutions as short as picoseconds have been achieved, but with respect to studies on the dynamics of supramolecular systems most studies used systems with nanosecond resolution. Laser irradiation is orthogonal to the monitoring beam used to measure the absorption of the sample before and after the laser pulse, leading to measurements of absorbance differences (AA) vs. time. Most laser flash photolysis systems are suitable to measure lifetimes up to hundreds of microseconds. Longer lifetimes are in general not accessible because of instabilities in the lamp of the monitoring beam and the fact that the detection system has been optimized for nanosecond experiments. 

With the invention of the laser in 1960 and the subsequent development of pulsed lasers using Q-switching (Chapter 1), monochromatic and highly-collimated light sources became available with pulse durations in the nanosecond timescale. These Q-switched pulsed lasers allow the study of photo-induced processes that occur some 103 times faster than events measured by flash lamp-based flash photolysis. 

As better and better methods for following fast reactions with precision were introduced and exploited, characteristic reaction times faster than a second— times measured in milhseconds (ms, 10 s), or microseconds (ps, 10 s), or nanoseconds (ns, 10 s) and then in picoseconds (ps, 10 s)—were measured through stopped-flow techniques (Chance, 1940), flash photolysis (Norrish and Porter, 1949), temperature-jump and related relaxation methods (Eigen, 1954), and then... 

In the nanosecond (ns) time-scale the use of kinetic detection (one absorption or emission wavelength at all times) is much more convenient than spectrographic detection, but the opposite is true for ps flash photolysis because of the response time of electronic detectors. Luminescence kinetics can however be measured by means of a special device known as the streak camera (Figure 8.2). This is somewhat similar to the cathode ray tube of an oscilloscope, but the electron gun is replaced by a transparent photocathode. The electron beam emitted by this photocathode depends on the incident light intensity I(hv). It is accelerated and deflected by the plates d which provide the time-base. The electron beam falls on the phosphor screen where the trace appears like an oscillogram in one dimension, since there is no jy deflection. The thickness of the trace is the measurement of light intensity. 

Bradaric and Leigh have also measured absolute rate constants for the reaction of a series of ring-substituted 1,1-diphenylsilene derivatives with methanol, f-butyl alcohol and acetic acid in acetonitrile by similar nanosecond laser flash photolysis techniques87 (Table 7). 

Nanosecond laser Flash Photolysis experiments were performed with 355 and 532 nm laser pulses from a Brilland-Quantel Nd YAG system (5 ns pulse width) in a front face (VIS) and side face (NIR) geometry using a pulsed 450 W XBO lamp as white light source. Similarly to the femtosecond transient absorption setup, a two beam arrangement was used. However, the pump and probe pulses were generated separately, namely the pump pulse stemming from the Nd YAG laser and the probe from the XBO lamp. A schematic representation of the setup is given below in Fig. 7.3. 0.5 cm quartz cuvettes were used for all measurements. 

Due to the fact that lasers can be focused into a very small volume, small slits can be used together with a fast rotating disk to make the time resolution in the one-slit experiment in the tens of nanoseconds when using very sensitive detection techniques and samples with good Raman enhancements. This technique will probably be most useful in the microsecond time regime. Fig. 1 shows the results of this technique when used in the measurement of the time development of the bands characteristic of the intermediates produced in the bacteriorhodopsin photosynthetic cycle (8). Using optical flash photolysis (17) techniques, the rise time of the intermediate having a Raman band at 1570 cm l is known to be in the microsecond time scale. 

Photophysical characteristics of Pis (Scheme 12.1), especially the quantum yields of their dissociation O iss, are very important. Most of the photophysical data were measured by nanoseconds or picoseconds laser flash photolysis (LFP) or phosphorescence at low temperature. The properties of representative Pis are given in Table 12.1. 

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