Femtosecond Detection Methods

The photolytic and probe pulses are colinear when they reach the sample. The photolytic pulse produces excited states and photofragments, and the probe pulse which follows closely behind must be used to analyse the concentration and/or the chemical nature of the transients. The major detection processes are known as laser-induced fluorescence (LIF) and multiphoton ionization (MPI). Transient absorptions can also be used in some cases, and this is similar to ps spectroscopy. 

LI Laser-induced Fluorescence. The probe wavelength Ap can be adjusted to excite one of the photofragments or the excited complex in the process of dissociation. Consider for instance the dissociation of a molecule AB according to 

2 Multiphoton Ionization. In some cases the probe pulse provides sufficient energy to ionize the fragments to form a positive ion and an electron. The positive ions can be detected in a mass spectrometer which replaces the 

These are essentially unimolecular reactions of dissociation and of isomerization, studied mostly in the gas phase. We shall consider here a few examples of such reactions. The dissociation of IGN can be written as 

There are other examples of such fast bond dissociations in the liquid phase, not necessarily hydrogen bonds. Thus the first step in the photo-chromic isomerization of spiropyrans (the ps events are shown in section 8.1.) is complete within 100 fs, that is within a single vibration of the bond. 

---

Contrary to the above-described detection methods, fluorescence up-conversion and optical Kerr gate techniques readily achieve picosecond/femtosecond time resolution (Ippen and Shank 1975 Shah 1988 Takeuchi and Tahara 1998), because they are in the pump-probe measurement, in principle. 

The time-resolved techniques that are usually used for FLIM are based on electronic-basis detection methods such as the time-correlated single photon counting or streak camera. Therefore, the time resolution of the FLIM system has been limited by several tens of picoseconds. However, fluorescence microscopy has the potential to provide much more information if we can observe the fluorescence dynamics in a microscopic region with higher time resolution. Given this background, we developed two types of ultrafast time-resolved fluorescence microscopes, i.e., the femtosecond fluorescence up-conversion microscope and the... 

Photocathode-based picosecond electron accelerators are conceptually simpler than pre-bunched thermionic systems, although they require reasonably powerful, multicomponent femtosecond or picosecond laser systems to drive the photocathode. In addition, the availability of synchronized laser pulses allows the development of advanced detection capabilities with unprecedented time resolution. The combination of ease of use and powerful detection methods has stimulated strong interest in photocathode gun systems. Since the installation ofthe first photocathode electron gun pulse radiolysis system at BNL [5,13], four additional photocathode-based facilities have become operational and two more are in progress. The operational centers include the ELYSE facility at the Universite de Paris-Sud XI in Orsay, France [7,8], NERL in Tokai-Mura, Japan [9,10], Osaka University [11,12], and Waseda University in Tokyo [13]. Facilities under development are located at the Technical University of Delft, the Netherlands, and the BARC in Mumbai, India. 

Laser-scanning microscopes can be classified by the way they excite and detect fluorescence in the sample. One-photon microscopes use a NUV or visible CW laser to excite the sample. Two-photon, or Multiphoton , microscopes use a femtosecond laser of high repetition rate. The fluorescence light can be detected by feeding it back through the scanner and through a confocal pinhole. The principle is termed confocal or descanned detection. A second detection method is to divert the fluorescence directly behind the microscope objective. The principle is termed direct or nondescaimed detection. 

A new era of research in fluorescence spectroscopy has emerged with the advent of powerful lasers capable of generating short-lived pulses and with the simultaneous development of sophisticated detection methods. While research groups were previously limited to the study of processes on the microsecond and nanosecond time scale, these developments have expanded the accessible time scale to the pico- and femtosecond. Time-resolved fluorescent measurements are being used, for example, to unravel the dynamics of excited states (excitons) generated in conjugated polymer films (such as stimulated emission) and the processes that... 

The conditions which determine whether flash photolysis can be used to smdy a given chemical system are (i) a precursor of the species of kinetic interest has to absorb light (normally from a pulsed laser) (ii) this species is produced on a timescale that is short relative to its lifetime in the system. Current technical developments make it easy to study timescales of nanoseconds for production and analysis of species, and the use of instrumentation with time resolution of picoseconds is already fairly common. In certain specific cases, as we will see in the last part of this chapter, it is possible to study processes on timescales greater than a few femtoseconds. Once the species of interest has been produced, it is necessary to use an appropriate rapid detection method. The most common technique involves transient optical absorption spectroscopy. In addition, luminescence has been frequently used to detect transients, and other methods such as time-resolved resonance Raman spectroscopy and electrical conductivity have provided valuable information in certain cases. 

In the time-domain detection of the vibrational coherence, the high-wavenumber limit of the spectral range is determined by the time width of the pump and probe pulses. Actually, the highest-wavenumber band identified in the time-domain fourth-order coherent Raman spectrum is the phonon band of Ti02 at 826 cm. Direct observation of a frequency-domain spectrum is free from the high-wavenum-ber limit. On the other hand, the narrow-bandwidth, picosecond light pulse will be less intense than the femtosecond pulse that is used in the time-domain method and may cause a problem in detecting weak fourth-order responses. 

In order to understand the dynamics of the solvent fluctuation, many experimental as well as theoretical efforts have been made intensively in the last decade. One of the most convenient methods to observe solvent reorganization relaxation processes within the excited state molecule is time resolved fluorescence spectroscopy. By using time resolved techniques a time dependent fluorescence peak shift, so ( ed dynamic Stokes shift, has been detected in nanosecond picosecond >, and femtosecond time regions. Another method to observe solvent relaxation processes is time resolved absorption spectroscopy. This method is suitable for the observation of the ground state recovery of the solvent orientational distribution surrounding a solute molecule. 

---