Picosecond Laser-Electron

To exploit the capabilities of fast lasers, a new picosecond Laser-Electron Accelerator Facility (LEAF) has been recently developed at Brookhaven National Laboratory. In this facility, schematically shown in Figure 1, laser light impinging on a photocathode inside a resonant cavity gun merely 30 cm in length produces the electron pulse. The emitted electrons are accelerated to energies of 9.2 MeV within that gun by a 15 MW pulse of RF power from a 2.9 GHz klystron. The laser pulse is synchronized with the RF power to produce the electron pulse near the peak field gradient (about 1 MeV/cm). Thus the pulse length and intensity are a function of the laser pulse properties, and electron... 

Hydrogen transfer in excited electronic states is being intensively studied with time-resolved spectroscopy. A typical scheme of electronic terms is shown in fig. 46. A vertical optical transition, induced by a picosecond laser pulse, populates the initial well of the excited Si state. The reverse optical transition, observed as the fluorescence band Fj, is accompanied by proton transfer to the second well with lower energy. This transfer is registered as the appearance of another fluorescence band, F2, with a large anti-Stokes shift. The rate constant is inferred from the time dependence of the relative intensities of these bands in dual fluorescence. The experimental data obtained by this method have been reviewed by Barbara et al. [1989]. We only quote the example of hydrogen transfer in the excited state of... 

The LIF technique is extremely versatile. The determination of absolute intermediate species concentrations, however, needs either an independent calibration or knowledge of the fluorescence quantum yield, i.e., the ratio of radiative events (detectable fluorescence light) over the sum of all decay processes from the excited quantum state—including predissociation, col-lisional quenching, and energy transfer. This fraction may be quite small (some tenths of a percent, e.g., for the detection of the OH radical in a flame at ambient pressure) and will depend on the local flame composition, pressure, and temperature as well as on the excited electronic state and ro-vibronic level. Short-pulse techniques with picosecond lasers enable direct determination of the quantum yield [14] and permit study of the relevant energy transfer processes [17-20]. 

Gratzel and Serpone and co-workers recently reported on a picosecond laser flash photolysis study of TiO. They observed the absorption spectrum immediately after the 30 ps flash and attributed it to electrons trapped on Ti" " ions at the surface of the colloidal particles. The absorption decayed within nanoseconds, the rate being faster as the number of photons absorbed per colloidal particle increased. This decay was attributed to the recombination of the trapped electrons with holes. 

By the late 1960s the development of mode locking (Chapter 1) allowed the study of picosecond laser techniques. Excited-state processes carried out in the picosecond domain allow such processes as intersystem crossing, energy transfer, electron transfer and many pho-toinduced unimolecular reactions to be investigated. 

When molecules absorb a photon and produce an electronic excited state, the energy can be dissipated in several ways luminescence, radiationless decay to the ground state, and photochemistry. Luminescence dominated the older literature because it was easy to observe. A good review of luminescence is in Volume 3 of David Dolphin s seven-volume series The Porphyrins. Picosecond laser spectroscopy allowed for exploration of the radiationless decay pathways, particularly the initial steps that compete with luminescence and lead to photochemistry. Two principal forms of radiationless decay lead to long-term metastables ligand ejection and electron transfer. 

Figure 1. Testing the Keldish limit [1, 2] to ionization by intense infrared femtosecond/picosecond laser pulses used for control of chemical reactions [3, 4], (a) Electronic ground state embedded in a typical model potential curve with the ionization potential Es = 12.9 eV. (b) Intense ( o = 35.5 GV/m"1, Iq = 3.3 x 1014 W/cm2), ultra-short (tp = 0.5 ps), infrared (l/X = 3784 cm" ) laser pulse, (c) Expectation value for the position of the election, which is driven by the laser held shown in panel (b) [compare with ro = 122 A, Eq. (3)]. (d) Electron energy. These model calculations demonstrate that even very intense (/ > /Keldish) ultrashort 1R laser pulses may not cause ionization that is, the simple estimates (1)—<4) [1, 2] are not applicable.

The development of synchrotron radiation as an X-ray source404 416 418 has permitted accumulation of data for electron density difference maps in less than 1 s and it is expected that such data can eventually be acquired in 1 ps.419-421 If a suitable photochemical reaction can be initiated by a picosecond laser flash, a substrate within a crystalline enzyme can be watched as it goes through its catalytic cycle. An example is the release of inorganic phosphate ions from a "caged phosphate" (Eq. 3-49) and study of the reaction of the released phosphate with glycogen phosphorylase (Chapter 12).422/423... 

On the fundamental side, the research on photocatalysis has focused on several topics, including a) the primary processes involved in the production and trapping of photogenerated electrons and holes, using pulsed femtosecond or picosecond laser techniques, b) measurements on the kinetics of the photodecomposition processes on longer time scales, and c) measurements on the kinetics on small size scales. For the first topic, the reader is referred to several recent publications.69-7 This work is of great practical importance, because it helps to point out the critical factors involved in the photocatalytic materials themselves. 

For DFWM and Z-scan with picosecond laser pulses molecular vibrations (or optical phonons in crystals) and reorientation of small molecules can add contributions to the electronic nonlinearity. For longer laser pulses even large molecules can orient and also thermal contributions can occur. 

Chen H, Soom B, Yaakobi B, Uchida S, Meyerhofer DD (1993) Hot-electron characterization from Ka measurements in high-contrast, p-polarized, picosecond laser-plasma interactions. Phys Rev Lett 70 3431-3434... 

The detection efficiency of C6H5X (X = F, Cl, Br and I) was investigated with the laser multiphoton ionization method152. The laser-induced ion yield depends mainly on the cross sections of the transitions available to the molecule ground state and on the lifetime of the intermediate electronic state that is initially excited. If a species has a radiative lifetime that is very short compared to the pulse duration, it may relax after excitation and will not be ionized. Molecular ions will therefore be obtained when laser pulses that are at least as short as the excited-state lifetimes are employed. The S excited states of halobenzenes are estimated to have subnanosecond lifetimes, with the exception of fluorobenzene for which a lifetime of the order of 9-10 ns has been calculated at 2ex = 266 nm. Picosecond laser pulses are therefore found effective in producing ionization of halobenzenes with short lifetimes, whereas nanosecond pulses are not152. 

The first picosecond laser spectroscopic study to examine charge carrier trapping and recombination dynamics was reported by Gratzel, Serpone and co-workers [15]. The mean lifetime of a single electron/hole pair was determined to be 30 15 ns at low occupancy of electron/hole pairs in the titanium dioxide particles. At high occupancies, where recombination followed second-order kinetics, the bulk rate coefficient for recombination was (3.2 1.4) x 10-11 cm3 s 1. 

Degenerate four-wave-mixing (DFWM, Section 10.2.3) in conjugated polymers has also been explored. Its use in optical image correlation has been demonstrated using Durham-route PAc and similar polymers. The very large optical non-linearity of PAc, Table 9.3, and the fast electronic response allow correlation to be performed with sub-picosecond laser pulses. The poor stability of PAc prevented this laboratory demonstration being turned into a practical device. 

Wang Y, Crawford MK, McAuliffe MJ, Eisenthal KB. (1980) Picosecond laser studies of electron solvation in alcohols. Chem Phys Lett 74 160-165. 

Marignier J-L, De Waele V, Monard H, Gobert F, Larbre J-P, Demarque A, Mostafavi M, Belloni J. (2006) Time-resolved spectroscopy at the picosecond laser-triggered electron accelerator ELYSE. Radiat Phys Ghent 75 1024-1033. 

Pulse-probe studies using the Laser Electron Accelerator Facility (LEAF) at Brookhaven National Laboratory have revealed changes in optical absorption occurring on the picosecond time scale in rare gas fluids. In xenon, excimers are formed which absorb in the visible and near infra-red as shown in Fig. la. The absorption grows in during the first 50 picoseconds [see Fig. 1(b)].This growth is concomitant with ion recombination that leads first to excited atoms, reaction 1(a), which immediately form excimers, Xe, because of the high density of xenon. 

James R Wishart received a B.S. in Chemistry from the Massachusetts Institute of Technology in 1979 and a Ph.D. in Inorganic Chemistry from Stanford University in 1985 under the direction of Prof Henry Taube. After a postdoctoral appointment at Rutgers University, in 1987 he joined the Brookhaven National Laboratory Chemistry Department as a Staff Scientist in the Radiation Chemistry Group. He founded and presently supervises the BNL Laser-Electron Accelerator Facility for picosecond electron pulse radiolysis. His research interests include ionic liquids, radiation chemistry, electron transfer, and new technology and techniques for pulse radiolysis. He has authored over 90 papers and chapters, and is the co-editor of Advances in Chemistry Series o. 254, Photoehemistry and Radiation Chemistry. 

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