Resonance fluorescence using pulsed excitation

IS, 8, Resonance fluorescence experiments using pulsed excitation... 

The detection of the fluorescence radiation differs in resonant and in non-resonant AFS. In the first case, the radiation is measured in a direction perpendicular to that of the incident exciting radiation. However the system will suffer from stray radiation and emission of the flame. The latter can be eliminated by using pulsed primary sources and phase-sensitive detection. In the case of non-resonant fluorescence, stray radiation problems are not encountered, although the fluorescence intensities are lower, which necessitates the use of lasers as primary sources and spectral apparatus that will isolate the fluorescence radiation. A set-up for laser excited AFS (Fig. 126) may make use of a pulsed dye laser pumped by an excimer laser. The selection of the excitation line is then done by the choice of the dye and... 

To set up the lifetime experiment, fluorescence excitation spectra were recorded using pulses of 90 ns duration corresponding to a spectral bandwidth of 15 MHz at a repetition rate of 1 MHz. The bandwidth was limited by the pulses rise and fall times, the pulse shapes and the frequency jitter of the laser. Fig. 8(a) shows a typical spectrum with four individual molecular resonances A, B, C and D. On average, the lines are about 25 MHz wide as compared to a homogeneous linewidth of about 8 MHz measured by earlier experiments using cw radiation and lower excitation energies. The best fit of the absorption profile of molecule C was obtained using a Lorentzian profile with a FWHM of 27 MHz. 

In most experiments, ultraviolet or infrared absorption, resonance fluorescence, or laser-induced fluorescence (LIF) is used to follow how transient concentrations change after the photolysis pulse. These optical techniques vary considerably in their sensitivity and hence to the extent to which they isolate the primary reaction. LIF is extremely sensitive, enabling one to follow decays of concentrations from an initial value of 10 ° cm , but its use is restricted to species with a bound-bound electronic transition within the range of tunable dye lasers. LIF has been used to follow the kinetics of reactions of, inter alia, the radicals OH [12-14], CN [15] and CH3O [16,17]. It is more difficult to apply to radical atoms vihich usually have allowed electronic transitions only in the vacuum ultraviolet. Some LIF measurements utilising two-photon excitation of atoms have been reported [18]. 

UV-excited Raman spectra of a number of synthetic polymers have been reported [29]. Raman spectra using pulsed laser output between 218 and 242 nm can be generated with very low power (< 1 mW) but care must be taken to prevent photo-oxidation and thermal degradation. UV resonance Raman spectra will be most valuable in the generation of fluorescence-free spectra for UV transparent polymers. 

Next we proceed to develop the theory o resonance fluorescence experiments using the ensemble density matrix to describe the system of atoms. The important concepts of optical and radio-frequency coherence and of the interference of atomic states are discussed in detail. As an illustration of this theory general expressions describing the Hanle effect experiments are obtained. These are evaluated in detail for the frequently employed example of atoms whose angular momentum quantum numbers in the ground and excited levels are J =0 and Jg=l respectively. Finally resonance fluorescence experiments using pulsed or modulated excitation are described. 

Introduction and experimental techniques. In previous sections we drew attention to the fact that, in both the classical and quantum theories, expressions derived for the intensity of resonance fluorescence from atoms subjected to an external magnetic field, equations (15,3) and (15.23) respectively, contain terms which may lead to a modulation of the intensity at the Larmor frequency or its second harmonic. This radio-frequency modulation has been observed in several different kinds of experiment, the simplest of which makes use of pulsed excitation and time-resolved detection of the fluorescent light. 

The wavelength of the probe pulse is tuned around 400 nm. This pulse resonantly excites the WP in the B state to the upper E state. Subsequent laser-induced fluorescence (LIT) from the E state is detected with a photomultiplier. We have utilized two kinds of probe lasers an fs laser and a nanosecond (ns) laser. If we use an fs probe pulse, the overall WP is resonantly excited from B io E states. The excitation predominantly occurs around a specific internuclear distance called a Franck-Condon point [37]. The Franck-Condon point r c is defined as... 

Figure 12-1. Schematic diagram to illustrate double resonance techniques, (a) REMPI 2 photon ionization. The REMPI wavelength is scanned, while a specific ion mass is monitored to obtain a mass dependent SI <- SO excitation spectrum, (b) UV-UV double resonance. One UV laser is scanned and serves as a burn laser, while a second REMPI pulse is fired with a delay of about 100 ns and serves as a probe . The probe wavelength is fixed at the resonance of specific isomer. When the burn laser is tuned to a resonance of the same isomer it depletes the ground state which is recorded as a decrease (or ion dip) in the ion signal from the probe laser, (c) IR-UV double resonance spectroscopy, in which the burn laser is an IR laser. The ion-dip spectrum reflects the ground state IR transitions of the specific isomer that is probed by the REMPI laser, (d) Double resonance spectroscopy can also use laser induced fluorescence as the probe, however that arrangement lacks the mass selection afforded by the REMPI probe...

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