Pulse-probe detection

Three different approaches have been employed to observe radiation-induced kinetics on the picosecond timescale. The first, pulse-probe detection, is covered in this section. Section 3.3 discusses a related technique that uses temporally-dispersed probe beams to record a kinetic trace in a single shot. Einally, Sec. 3.4... 

Fig. 11. Schematic of the picosecond pulse-probe detection system at NERL, University of Tokyo.

With the advent of laser-pulsed photocathode accelerators, a new approach to pulse-probe detection is possible. Spare output from the laser system used to generate the photoelectrons can be used to create a probe beam synchronized to the electron pulse with resolution on the order of 100 fs. Optical parametric... 

Reference PD B Electron Beam Figure 6. Schematic representation of the LEAF pulse-probe detection system. 

The limitations to the time resolution are the length of the excitation pulse, the time resolution of the detection equipment and the speed of the chemistry creating the reactants of interest. With lasers presently available with pulse widths less than a picosecond, the pulse length is not a major limitation. Using a pulse-probe detection technique, the only limitation of Ae time resolution may be the formation of the desired reactant. 

As an example, we mention the detection of iodine atoms in their P3/2 ground state with a 3 + 2 multiphoton ionization process at a laser wavelength of 474.3 run. Excited iodine atoms ( Pi/2) can also be detected selectively as the resonance condition is reached at a different laser wavelength of 477.7 run. As an example, figure B2.5.17 hows REMPI iodine atom detection after IR laser photolysis of CF I. This pump-probe experiment involves two, delayed, laser pulses, with a 200 ns IR photolysis pulse and a 10 ns probe pulse, which detects iodine atoms at different times during and after the photolysis pulse. This experiment illustrates a frindamental problem of product detection by multiphoton ionization with its high intensity, the short-wavelength probe laser radiation alone can photolyse the... 

Many methods of investigation of protein-ligand binding kinetics that are based on linear processes are of a pump-probe type. In this approach an optical pulse, called a pump, starts a photoreaction (such as dissociation of MbCO into Mb and CO), and its progress is probed a time At later. The probe could be, for example, a weak laser pulse, which detects the spectral changes in the heme during the protein-ligand recombination, or an x-ray pulse, which allows determination of the protein structure at a particular instant in time. 

The subpicosecond pulse radiolysis [74,77] detects the optical absorption of short-lived intermediates in the time region of subpicoseconds by using a so-called stroboscopic technique as described in Sec. 10.2.2 ( History of Picosecond and Subpicosecosecond Pulse Radiolysis ). The short-lived intermediates produced in a sample by an electron pulse are detected by measuring the optical absorption using a very short probe light (a femtosecond laser in our system). The time profile of the optical absorption can be obtained by changing the delay between the electron pulse and the probe light. 

Figure 19.1. Schematic diagram of a general pump-probe-detect laser spectrometer suitable for picosecond electronic absorption, infrared (IR) absorption, Raman, optical calorimetry, and dichroism measurements. For picosecond fluorescence—a pump-detect method, no probe pulse needs to be generated.

Figure 20.2. Schematic outline of typical pump-probe-detect experiments with femtosecond pulses, a molecular beam source, and mass spectrometric detection of transient species. Computer control and data processing instruments, as well as various optical components, are not shown. The time separation Af between pump and probe pulses is dictated by the difference in optical path lengths. Ad, traversed by the two components of the original pulse.

The pump-probe-detect arrangements for the femtosecond experiments was similar to those described above. When cyclobutanone was pumped with two photons of a X = 307-nm femtosecond pulse, two consecutive C—CO bond cleavages led to the formation of the trimethylene diradical, detected as an easily ionized transient at 42 amu, with buildup and decay times of 120 20 fs. The decay presumably involves isomerizations to cyclopropane and to propylene— structures not ionized by the probe pulse and thus undetected during the experiment. 

S02)n clusters were excited by one and two photon absorption of the 265 nm pump pulse. The excited state clusters were then ionized at incremental delay times by the 398 nm probe pulse, allowing detection by mass spectrometry. 

The extent of gas dispersion can usually be computed from experimentally measured gas residence time distribution. The dual probe detection method followed by least square regression of data in the time domain is effective in eliminating error introduced from the usual pulse technique which could not produce an ideal Delta function input (Wu, 1988). By this method, tracer is injected at a point in the fast bed, and tracer concentration is monitored downstream of the injection point by two sampling probes spaced a given distance apart, which are connected to two individual thermal conductivity cells. The response signal produced by the first probe is taken as the input to the second probe. The difference between the concentration-versus-time curves is used to describe gas mixing. 

Detection Pulse-probe Pulse-probe High dynamic Pulse-probe Pulse-probe [30] Pulse-probe... 

The various probe beams can be coupled into the same singlewavelength, dual-channel pulse-probe transient optical absorption set-up. A one-meter-long optical delay line is used to control the variable time delay between the electron and the probe pulses. Approximately half of the probe beam is deflected onto a reference photodiode while the other half of the beam is slightly focused into the sample, which is placed in front of the output window of the accelerator. Subsequently, the probe beam is then transported to the sample photodiode. (Alternatively, in some laboratories the probe and reference beams are transported into the detection room by long, low-OH silica optical fibers in order to reduce electronic noise pickup on the detector signal cables.)... 

Thanks to the advent of sophisticated accelerators and detection systems, pulse-probe pulse radiolysis experiments have become widely used to explore very fast chemical events and to answer questions about the inhomogeneous chemistry that occurs at early times following... 

Pulse-probe pulse radiolysis detection techniques are very powerful, however to obtain kinetic profiles of fast reactions they all rely to... 

There are two interesting regimes of time evolution in the probing/detection of dynamical nonequilibrium structures. In the regime of dynamics, the time evolution of atomic positions is detected on its intrinsic timescale, i.e., femtoseconds. Short X-ray pulses - on the timescale of atomic motion - are required in order to follow the dynamics of the chemical bond. In the regime of kinetics, which has to do with the time evolution of populations - and in the context of time-resolved X-ray diffraction -the time evolution in an ensemble average of different interatomic distances or the structural determination of short-lived chemical species is considered. 

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. 

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