Short-pulse lasers

With the advent of short pulsed lasers, investigators were able to perfonn time resolved coherent Raman scattering. In contrast to using femtosecond pulses whose spectral widtii provides the two colours needed to produce Raman coherences, discussed above, here we consider pulses having two distinct centre frequencies whose difference drives the coherence. Since the 1970s, picosecond lasers have been employed for this purpose [113. 114], and since the late 1980s femtosecond pulses have also been used [115]. Flere we shall briefly focus on the two-colour femtosecond pulsed experiments since they and the picosecond experiments are very similar in concept. 

The dynamics of fast processes such as electron and energy transfers and vibrational and electronic deexcitations can be probed by using short-pulsed lasers. The experimental developments that have made possible the direct probing of molecular dissociation steps and other ultrafast processes in real time (in the femtosecond time range) have, in a few cases, been extended to the study of surface phenomena. For instance, two-photon photoemission has been used to study the dynamics of electrons at interfaces [ ]. Vibrational relaxation times have also been measured for a number of modes such as the 0-Fl stretching m silica and the C-0 stretching in carbon monoxide adsorbed on transition metals [ ]. Pump-probe laser experiments such as these are difficult, but the field is still in its infancy, and much is expected in this direction m the near fiitiire. 

With the short pulses available from modem lasers, femtosecond time resolution has become possible [7, 71, 72 and 73], Producing accurate time delays between pump and probe pulses on this time scale represents a... 

Figure C3.3.4 shows a schematic diagram of an apparatus tliat can be used to study collisions of tlie type described above [5, 9,12,16]. Donor molecules in a 3 m long collision cell (a cylindrical tube) are excited along tlie axis of tlie cell by a short-pulse excimer laser (typically 25 ns pulse widtli operating at 248 mil), and batli molecules are probed along tliis same axis by an infrared diode laser (wavelengtli in tlie mid-infrared witli continuous light-output...

The timing of the emission is clearly dependent on the system in use. For example, if pumping is relatively slow and stimulated emission is fast, then the emergent beam of laser light will appear as a short pulse (subsequent lasing must await sufficient population inversion). This behavior is... 

For many lasers used in scientific work, the light is emitted in a short pulse lasting only a few nanoseconds, but the pulses can be repeated at very short intervals. Other lasers produce a continuous output of light. 

From the Heisenberg uncertainty principle as stated in Equation (1.16) estimate, in cm and Hz, the wavenumber and frequency spread of pulsed radiation with a pulse length of 30 fs, typical of a very short pulse from a visible laser, and of 6 ps, typical of pulsed radiofrequency radiation used in a pulsed Fourier transform NMR experiment. 

In 1991 a remarkable discovery was made, accidentally, with a Tp -sapphire laser pumped with an Ar+ laser. Whereas we would expect this to result in CW laser action, when a sharp jolt was given to the table supporting the laser, mode locking (Section 9.1.5) occurred. This is known as self-locking of modes, and we shall not discuss further the reasons for this and how it can be controlled. One very important property of the resulting pulses is that they are very short. Pulse widths of a few tens of femtoseconds can be produced routinely and with high pulse-to-pulse stability. Further modification to the laser can... 

Another variation is the mode-locked dye laser, often referred to as an ultrafast laser. Such lasers offer pulses having durations as short as a few hundred femtoseconds (10 s). These have been used to study the dynamics of chemical reactions with very high temporal resolution (see Kinetic LffiASURELffiNTS). 

The availability of lasers having pulse durations in the picosecond or femtosecond range offers many possibiUties for investigation of chemical kinetics. Spectroscopy can be performed on an extremely short time scale, and transient events can be monitored. For example, the growth and decay of intermediate products in a fast chemical reaction can be followed (see Kinetic measurements). 

J.S. Wark, R.R. Whitlock, A. Hauer, J.E. Swain, and P.J. Solone, Short-Pulse X-Ray Diffraction from Laser-Shocked Crystals, in Shock Waves in Condensed Matter 1987 (edited by S.C. Schmidt and N.C. Holmes), Amsterdam, 1988, pp. 781-786, Elsevier Science. 

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 events that happen to an atom in a chemical reaction are on a time scale of approximately 1 femtosecond (1 fs = 10 ",5 s), the time that it takes for a bond to stretch or bend and, perhaps, break. If we could follow atoms on that time scale, we could make a movie of the changes in molecules as they take part in a chemical reaction. The new field of femto-cbemistry, the study of very fast chemical processes, is bringing us closer to realizing that dream. Lasers can emit very intense but short pulses of electromagnetic radiation, and so they can be used to study processes on very short time scales. 

In studies of molecular dynamics, lasers of very short pulse lengths allow investigation by laser-induced fluorescence of chemical processes that occur in a picosecond time frame. This time period is much less than the lifetimes of any transient species that could last long enough to yield a measurable vibrational spectrum. Such measurements go beyond simple detection and characterization of transient species. They yield details never before available of the time behavior of species in fast reactions, such as temporal and spatial redistribution of initially localized energy in excited molecules. Laser-induced fluorescence characterizes the molecular species that have formed, their internal energy distributions, and their lifetimes. 

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]. 

In the 1960s, Oppenheim et al. [10,19,20] succeeded in obtaining photographs with better resolution by means of schlieren technique with microsecond flash and then with the very short (less than 10 s) laser light pulses. This facilitated the attainment of a stroboscopic set of essentially still photographs that revealed many details of DDT. At the same time, Soloukhin [21] published a series of streak photographs taken with schlieren system and Denisov and Troshin [22] discovered that detonation leaves a record of its passage in the form of imprint on a wall coated with the thin layer of soot. 

Vibrational and Electronic Excitation of Molecules by Short-Pulse Strong Laser Fields... 

An alternative way to preform a channeled plasma consists in exploiting the nanosecond precursor that usually precedes a short femtosecond pulse in the output of a multi-terawatt laser system. In fact, the amplified spontaneous emission (ASE) pedestal has typically an intensity 106-1010 times lower than the main pulse, which, however, can be sufficient to ionize a gas-jet or a solid target. This drawback can be turned into a benefit assuming that this long precursor can prepare the plasma channel for the short pulse propagation. 

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