Laser pulse irradiation

For the techniques using very short, high irradiance laser pulses, a more or less smooth transition to pyrolysis of the sample is observed with increasing irradiance. It appears that at least for the LAMMA technique this transition does not always occur at identical irradiances for positive and negative ions. This will be discussed in more detail later in this paper. 

In the present section, we concentrate on coherent preparation by irradiation with a properly chosen laser pulse during a given time interval. The quantum state at time t may be chosen to be the vibrational ground... 

In Laser Ionization Mass Spectrometry (LIMS, also LAMMA, LAMMS, and LIMA), a vacuum-compatible solid sample is irradiated with short pulses ("10 ns) of ultraviolet laser light. The laser pulse vaporizes a microvolume of material, and a fraction of the vaporized species are ionized and accelerated into a time-of-flight mass spectrometer which measures the signal intensity of the mass-separated ions. The instrument acquires a complete mass spectrum, typically covering the range 0— 250 atomic mass units (amu), with each laser pulse. A survey analysis of the material is performed in this way. The relative intensities of the signals can be converted to concentrations with the use of appropriate standards, and quantitative or semi-quantitative analyses are possible with the use of such standards. 

The material evaporated by the laser pulse is representative of the composition of the solid, however the ion signals that are actually measured by the mass spectrometer must be interpreted in the light of different ionization efficiencies. A comprehensive model for ion formation from solids under typical LIMS conditions does not exist, but we are able to estimate that under high laser irradiance conditions (>10 W/cm ) the detection limits vary from approximately 1 ppm atomic for easily ionized elements (such as the alkalis, in positive-ion spectroscopy, or the halogens, in negative-ion spectroscopy) to 100—200 ppm atomic for elements with poor ion yields (for example, Zn or As). 

When Ss solutions in cyclopentane (1 mmol 1 ) were irradiated by 308 nm laser pulses four novel absorption bands at 325, 400, 530, and 640 nm appeared [50]. The absorptions assigned to S3 (400 nm) and S4 (530 nm) decayed within microseconds. The other two peaks also disappeared very rapidly but their origin remained unexplained in 1985. However, it is now evident that the 640 nm absorption is due to the presence of the C2h isomer of S4. Evidently, Ss decomposes by the following reactions ... 

It is useful for illustrative purposes to consider a laser beam with a Gaussian spatial profile and a square pulse time profile. If the laser has a Gaussian spatial beam profile the temperature at the surface of the Irradiated solid (z=0) at a time t after the laser pulse is started is given by(4) ... 

In the laser flash method, the heat is put in by laser flash instead of electric current in the stepwise heating method mentioned above. Thus this method may be classified as a stepwise heating method. A two-layered laser flash method was developed by Tada et al. " The experimental method and the data analysis, including a case involving radiative heat flow, are described in detail in the review article by Waseda and Ohta. A thin metal plate is placed at the surface of a melt. A laser pulse is irradiated onto a metal plate of thickness / having high thermal conductivity. The sample liquid under the metal plate and the inert gas above the plate are designated as the third and first layers, respectively. The temperature of the second layer becomes uniform in a short time" and the response thereafter is expressed by... 

In the laser flash method, a melt of interest is placed between two parallel plates. The upper plate is heated stepwise and the thermal diffusiv-ity is measured from the rise in temperature. The specific design for molten materials and especially slags employed by Ohta et al. is based on the differential three-layer technique utihzing a special cell that can be accommodated in the system. A schematic diagram of the principle of the measurement section is shown in Fig. 31. A laser pulse irradiates the upper (platinum) crucible and the temperature response of the surface of the lower platinum crucible is observed, a liquid specimen being sandwiched between the two. 

Photoinduced oxidation of 1,4-dimethoxybenzene (DMB) and tetrahydrofuran (THF) by [Au(C N N-dpp)Cl]+ in acetonitrile upon UV/Vis irradiation have been observed. The time-resolved absorption spectrum recorded 12 (xs after excitation of [Au(C N N-dpp)Cl] with a laser pulse at 35 5 nm showed the absorption band of the DMB radical cation at 460nm, whereas upon excitation at 406 nm in the presence of THF, a broad emission characteristic of the protonated salt of 2,9-diphenyl-l,10-phenanthroline (Hdpp ) developed at 500 nm. 

Noguchi, H., Okada, T, Onda, K., Kano, S. S., Wada, A. and Domen, K. (2003) Time-resolved SFG study of formate on a Ni(lll) surface under irradiation of picosecond laser pulses. Surf. Sci., 528, 183-188. 

Figure 8.2a-c shows optical transmission images of organic microcrystals of perylene, anthracene, and pyrene, excited at a laser power of 1.7 nj pulse under similar excitation conditions as in Figure 8.1c. The bright spots <2 pm in diameter at the center of each microcrystal were areas irradiated with the NIR laser pulse.

Figure 8.3 Interferometric autocorrelation traces of the fluorescence intensities of perylene (a) and anthracene (b) microcrystals irradiated by two NIR Cr F laser pulses centered at 1.26 Xm with the same intensity.

Final resolution of these problems, particularly the complications from multiple matrix sites, came from investigations using spectroscopic methods with higher time resolution, viz. laser flash photolysis. Short laser pulse irradiation of diazofluorene (36) in cold organic glasses produced the corresponding fluorenylidene (37), which could be detected by UV/VIS spectroscopy. Now, in contrast to the results from EPR spectroscopy, single exponential decays of the carbene could be observed in matrices... 

If the EDA and CT pre-equilibria are fast relative to such a (follow-up) process, the overall second-order rate constant is k2 = eda c e In this kinetic situation, the ion-radical pair might not be experimentally observed in a thermally activated adiabatic process. However, photochemical (laser) activation via the deliberate irradiation of the charge-transfer absorption (hvct) will lead to the spontaneous generation of the ion-radical pair (equations 4, 5) that is experimentally observable if the time-resolution of the laser pulse exceeds that of the follow-up processes (kf and /tBet)- Indeed, charge-transfer activation provides the basis for the experimental demonstration of the viability of the electron-transfer paradigm in Scheme l.21... 

In summary, the main issues were presented here concerning experimental investigation of fast-electron transport in solids irradiated at ultra-high intensity using high-power, femtosecond laser pulses. A discussion was given on... 

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. 

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