Pump-probe laser technique

The electronic structure of fluorenes and the development of their linear and nonlinear optical structure-property relationships have been the subject of intense investigation [20-22,25,30,31]. Important parameters that determine optical properties of the molecules are the magnitude and alignment of the electronic transition dipole moments [30,31]. These parameters can be obtained from ESA and absorption anisotropy spectra [32,33] using the same pump-probe laser techniques described above (see Fig. 9). A comprehensive theoretical analysis of a two beam (piunp and probe) laser experiment was performed [34], where a general case of induced saturated absorption anisotropy was considered. From this work, measurement of the absorption anisotropy of molecules in an isotropic ensemble facilitates the determination of the angle between the So Si (pump) and Si S (probe) transitions. The excited state absorption anisotropy, rabs> is expressed as [13] ... 

Photodissociation dynamics [89,90] is one of the most active fields of current research into chemical physics. As well as the scalar attributes of product state distributions, vector correlations between the dissociating parent molecule and its photofragments are now being explored [91-93]. The majority of studies have used one or more visible or ultraviolet photons to excite the molecule to a dissociative electronically excited state, and following dissociation the vibrational, rotational, translational, and fine-structure distributions of the fragments have been measured using a variety of pump-probe laser-based detection techniques (for recent examples see references 94-100). Vibrationally mediated photodissociation, in which one photon... 

Ultrafast molecular elimination of iodine from IF2C-CF2I has been studied using the velocity map ion imaging technique in combination with femtosecond pump-probe laser excitation.51 By varying the femtosecond delay between pump and probe pulse, it has been found that elimination of molecular iodine is a concerted process, although the two carbon-iodine bonds are not broken synchronously. 

A simplified view of the early processes in electron solvation is given in Figure 7. Initially, electron pulse radiolysis was the main tool for the experimental study of the formation and dynamics of electrons in liquids (Chapter 2), first in the nanosecond time range in viscous alcohols [23], later in the picosecond time range [24,25]. Subsequently, laser techniques have achieved better time resolution than pulse radiolysis and femtosecond pump-probe laser experiments have led to observations of the electron solvation on the sub-picosecond to picosecond time scales. The pioneering studies of Migus et al. [26] in water showed that the solvation process is complete in a few hundreds of femtoseconds and hinted at the existence of short-lived precursors of the solvated electron, absorbing in the infrared spectral domain (Fig. 8). The electron solvation process could thus be depicted by sequential stepwise relaxation cascades, each of the successive considered species or... 

For measuring the transient photoexcitation response in the Is to ns time domain we have used the fs two-color pump-probe correlation technique with linearly polarized light beams. We have used two laser systems a high repetition rate, low power laser for the mid-lR spectral range [92] and a relatively lower repetition rate, high power laser system for the near-lR and visible spectral range [93]. 

I PUMP-PROBE SPECTROSCOPY TECHNIQUES AND PHOTODYNAMICS TL NONLINEAR LASER SPECTROSCOPY AND MOLECULAR MOTION... 

At still shorter time scales other techniques can be used to detenuiue excited-state lifetimes, but perhaps not as precisely. Streak cameras can be used to measure faster changes in light intensity. Probably the most iisellil teclmiques are pump-probe methods where one intense laser pulse is used to excite a sample and a weaker pulse, delayed by a known amount of time, is used to probe changes in absorption or other properties caused by the excitation. At short time scales the delay is readily adjusted by varying the path length travelled by the beams, letting the speed of light set the delay. 

B2.5.4.2 LASER FLASH PHOTOLYSIS AND PUMP-PROBE TECHNIQUES... 

Figure B2.5.8. Schematic representation of laser-flash photolysis using the pump-probe technique. The beam splitter BS splits the pulse coming from the laser into a pump and a probe pulse. The pump pulse initiates a reaction in the sample, while the probe beam is diverted by several mirrors M tluough a variable delay line.

In many respects the time-resolved pump-probe technique is similar to the CW counterpart. The use of pulsed laser light permits direct probing of both the magnitude of the PA and its dynamics. The experimental arrangement is practically the same as for the CW version, i.e., both pump and probe beams are focused and overlapped onto same spot on a sample. In addition, the pump and probe pulses are synchronized so that the lime interval t between them is constant and confined to a certain time range (in our case up to 3 ns). 

Absorption and Ensuing Ion-Molecule Reactions via Ultrafast Laser Pump-Probe Techniques.196... 

Another very informative nonlinear experiment involves a typical pump-probe technique, but with varying laser polarization. These experiments, again for isolated chromophores, measure the rotational anisotropy TCF [122]... 

A typical application is the use of the (2 + 1) REMPI scheme for measuring the (v,./) distribution of H2 produced in associative desorption from a surface. When the laser is tuned to a spectroscopic transition between individual quantum states in the X -> E electronic band, resonant two-photon absorption populates the E state and this is subsequently ionized by absorption of another photon. The ion current is proportional to the number in the specific (v,./) quantum state in the ground electronic state that is involved in the spectroscopic transition. Tuning the laser to another spectroscopic feature probes another (v, J) state. Therefore, recording the ion current as the laser is scanned over the electronic band maps out the population distribution of H2(v, J) produced in the associative desorption. Ef of the (v, J) state can also often be simultaneously measured using field - free ion TOF or laser pump - probe TOF detection techniques. The (2 +1) REMPI scheme for detecting H2 is almost independent of the rotational alignment and orientation f(M) of molecules so that only relative populations of the internal states... 

The solutions were photolyzed by 266 nm quanta of a Nd YAG laser (FWHM < 3ns, energies up to 15 mJ) equipped with an optical absorption detection setup and by 253 nm quanta of a 10 Hz Ti Sapphire laser system generating 250 fs pulses up to 2 mJ at 253 nm. Absorption measurements were performed by the pump-probe technique. 

The experimental configuration of the pump-probe experiment is similar to Ref. [5]. A home built non-collinear optical parametric amplifier (nc-OPA) was used as a pump, providing Fourier-transform-limited 30 fs pulses, which could be spectrally tuned between 480-560 nm. In all experiments white-light generated in a sapphire crystal using part of the fundamental laser (800 nm), was used as probe light. In the pump-probe experiments the pump was tuned to the S2 0-0 band for carotenoids with n>l 1. In the case of M9, it was not possible to tune the nc-OPA to its 0-0 transition, and hence another nc-OPA tuned to 900 nm was frequency doubled and used for excitation. In addition to conventional transient absorption pump-probe measurements, we introduce pump-deplete-probe spectroscopy, which is sensitive to the function of an absorbing state within the deactivation network. In this technique, we... 

We have employed this phase-sensitive pump-probe technique to further investigate the multiphoton ionization of Na2 with 618-nm femtosecond pulses as discussed in the previous paragraph and have observed the interference of the A E and 2 Tlg wavepackets created by the first pulse and those created by the second pulse in the Na2+ signal. The amplitude of the high-frequency oscillations in the Na2+ signal was obtained as a function of pump-probe delay by filtering the transient with the laser frequency. It is shown in Fig. 8 (top). Below the averaged Na2+ transient of Fig. 4 is... 

On the other hand, additional spectroscopic information can be obtained by making use of this technique The Fourier transform of the frequency-filtered transient (inset in Fig. 8) shows that the time-dependent modulations occur with the vibrational frequencies of the A E and the 2 IIg state. In the averaged Na2+ transient there was only a vanishingly small contribution from the 2 IIg state, because in the absence of interference at the inner turning point ionization out of the 2 IIg state is independent of intemuclear distance, and this wavepacket motion was more difficult to detect. In addition, by filtering the Na2+ signal obtained for a slowly varying pump-probe delay with different multiples of the laser frequency, excitation processes of different order may be resolved. This application is, however, outside the scope of this contribution and will be published elsewhere. 

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