Absorption tunable

In Y3A1 0]2 the lowest 5d band is located below So and fluoresces with high quantum efficiency at temperatures 300 K (49). Several intense 4f5d- 4f2 transitions in the nearultraviolet could provide tunable laser action barring strong excited-state absorption. Tunable laser action in the 215-260 nm range in LiYF4 may also be possible (50). 

The development of ultrafast spectroscopy has paralleled progress in the teclmical aspects of pulse fomiation [Uj. Because mode-locked laser sources are tunable only with diflSculty, until recently the most heavily studied physical and chemical systems were those that had strong electronic absorption spectra in the neighbourhood of conveniently produced wavelengths. 

Recently, the state-selective detection of reaction products tluough infrared absorption on vibrational transitions has been achieved and applied to the study of HF products from the F + H2 reaction by Nesbitt and co-workers (Chapman et al [7]). The relatively low sensitivity for direct absorption has been circumvented by the use of a multi-pass absorption arrangement with a narrow-band tunable infrared laser and dual beam differential detection of the incident and transmission beams on matched detectors. A particular advantage of probing the products tluough absorption is that the absolute concentration of the product molecules in a given vibration-rotation state can be detenuined. 

In the microwave region tunable monochromatic radiation is produced by klystrons, each one being tunable over a relatively small frequency range, or a backward wave oscillator, tunable over a much larger range. Both are electronic devices. Absorption experiments are usually carried out in the gas phase, and mica windows, which transmit in this region, are placed on either end of the absorption cell, which may be several metres in length. Stark... 

Electronic transitions in molecules in supersonic jets may be investigated by intersecting the jet with a tunable dye laser in the region of molecular flow and observing the total fluorescence intensity. As the laser is tuned across the absorption band system a fluorescence excitation spectrum results which strongly resembles the absorption spectrum. The spectrum... 

Laser Photochemistry. Photochemical appHcations of lasers generally employ tunable lasers which can be tuned to a specific absorption resonance of an atom or molecule (see Photochemical technology). Examples include the tunable dye laser in the ultraviolet, visible, and near-infrared portions of the spectmm the titanium-doped sapphire, Tfsapphire, laser in the visible and near infrared optical parametric oscillators in the visible and infrared and Line-tunable carbon dioxide lasers, which can be tuned with a wavelength-selective element to any of a large number of closely spaced lines in the infrared near 10 ]lni. 

The existence of isotope shifts and of tunable lasers with narrow Hnewidth leads to the possibHity of separating isotopes with laser radiation (113,114). This can be of importance, because isotopicaHy selected materials are used for many purposes in research, medicine, and industry. In order to separate isotopes, one needs a molecule that contains the desired element and has an isotope shift in its absorption spectmm, plus a laser that can be tuned to the absorption of one of the isotopic constituents. Several means for separating isotopes are avaHable. The selected species may be ionized by absorption of several photons and removed by appHcation of an electric field, or photodissociated and removed by chemical means. 

Absorption spectroscopy records depletion by the sample of radiant energy from a continuous or frequency-tunable source, at resonance frequencies that are characteristic of various energy levels ia atoms or molecules. The basic law of absorption, credited to Bouguer-Lambert-Beer, states that ia terms of the iacident, Jq, and transmitted, light iatensities, the absorbance, M (or transmittance, T), is given by equation 1 ... 

Vj = 1 <— v" = 1 transition will be at a different energy than the Vj = 0 <— v" = 0. We use this fact to measure the vibrational spectrum of V (OCO) in a depletion experiment (Fig. 12a). A visible laser is set to the Vj = 0 Vj = 0 transition at 15,801 cm producing fragment ions. A tunable IR laser fires before the visible laser. Absorption of IR photons removes population from the ground state, which is observed as a decrease in the fragment ion signal. This technique is a variation of ion-dip spectroscopy, in which ions produced by 1 + 1 REMPI are monitored as an IR laser is tuned. Ion-dip spectroscopy has been used by several groups to study vibrations of neutral clusters and biomolecules [157-162]. 

The general principle of detection of free radicals is based on the spectroscopy (absorption and emission) and mass spectrometry (ionization) or combination of both. An early review has summarized various techniques to detect small free radicals, particularly diatomic and triatomic species.68 Essentially, the spectroscopy of free radicals provides basic knowledge for the detection of radicals, and the spectroscopy of numerous free radicals has been well characterized (see recent reviews2-4). Two experimental techniques are most popular for spectroscopy studies and thus for detection of radicals laser-induced fluorescence (LIF) and resonance-enhanced multiphoton ionization (REMPI). In the photochemistry studies of free radicals, the intense, tunable and narrow-bandwidth lasers are essential for both the detection (via spectroscopy and photoionization) and the photodissociation of free radicals. 

For 2PA or ESA spectral measurements, it is necessary to use tunable laser sources where optical parametric oscillators/amplifiers (OPOs/OPAs) are extensively used for nonlinear optical measurements. An alternative approach, which overcomes the need of expensive and misalignment prone OPO/OPA sources, is the use of an intense femtosecond white-light continuum (WLC) for Z-scan measurements [71,72]. Balu et al. have developed the WLC Z-scan technique by generating a strong WLC in krypton gas, allowing for a rapid characterization of the nonlinear absorption and refraction spectra in the range of 400-800 nm [72]. 

Four different laboratories have built IR kinetic spectrometers for use with organometallic compounds. A fundamental feature of all these spectrometers is that the detector is AC coupled. This means that the spectrometers only measure changes in IR absorption. Thus, in the time-resolved IR spectrum, bands due to parent compounds destroyed by the flash appear as negative absorptions, bands due to photoproducts appear as positive absorptions, and static IR absorptions, due to solvents, for example, do not register at all. The important features of these spectrometers are listed in Fig. 2. Since three spectrometers have a line-tunable CO laser as the monochromatic light source, we begin with the CO laser. Then we look in more detail at spectrometers designed for gas phase and solution experiments. 

Stability may not be as much of a problem as with a diode source. However, there are problems with this method as well. The range of tunability is limited by the absorption properties of the nonlinear crystal which generates the difference frequency. At present, tunability is limited to wavenumbers >2500 cm-1 and conversion efficiencies are low. Typical laser powers in the CH2 experiments (82) were 20 n W (compared to the power of the CO lasers, 10 mW-1 W). This produces a situation where IR detectors, particularly fast ones, may be close to or background noise limited. However, it is clear that more applications of this technique will appear in the future. 

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