Photons laser-induced fluorescence

The photolysis of methyl nitrite at low temperature in an argon matrix was studied157. The products include formaldehyde, and nitroxyl HNO which also reacts to form N2O and water. The 355-nm photodissociation of gaseous methyl nitrite has been studied by monitoring the nascent NO product using a two-photon laser-induced fluorescence... 

Bradshaw, J. D., M. O. Rodgers, S. T. Sandholm, S. KeSheng, and D. D. Davis, A Two-Photon Laser-Induced Fluorescence Field Instrument for Ground-Based and Airborne Measurements of Atmospheric NO, J. Geophys. Res., 90, 12861-12873 (1985). 

Sandholm, S., S. Smyth, R. Bai, and J. Bradshaw, Recent and Future Improvements in Two-Photon Laser-Induced Fluorescence NO Measurement Capabilities, J. Geophys. Res., 102, 28651-28661 (1997). 

Here we present the latest results from our group focused on the design of tailored femtosecond pulses to achieve control of nonlinear optical excitation in large molecules based on the concept of multiphoton intrapulse interference (Mil) [1-4]. Our goal is to elucidate well-defined and reproducible pulse shapes that can be used to enhance or suppress particular nonlinear optical transitions in large molecules such as laser dyes and proteins in solution. We demonstrate the use of Mil to probe the local and microscopic environment of molecules by selective two-photon laser induced fluorescence (LIF). 

A sensor based on two-photon laser-induced fluorescence has been described for detection of N0-N0r-N02 (72). NO is detected directly on the basis of its fluorescent properties. N02 is first converted to NO by photo-... 

Lozovoy VV, Pastirk I, Walowicz KA, Dantus M (2003) Multiphoton intrapulse interference. II. Control of two- and three-photon laser induced fluorescence with shaped pulses. J Chem Phys 118 3187... 

Kim NJ, Jeong G, Kim YS, Sung J, Kim SK, Park YD (2000) Resonant two-photon ionization and laser induced fluorescence spectroscopy of jet-cooled adenine. J Chem Phys 113 10051... 

Valuable findings on the electronic ground and excited states of clusters have been derived from laser-induced multi-photon ionization (MPl) investigations, such as laser-induced fluorescence (LIF) and REMPI. This latter technique is particularly promising since it enables mass selection of cluster species and their spectral and thermochemical characterization. The complex is excited from its electronic ground state from a photon and then ionized by a second photon of equal or different frequency, near threshold to avoid cluster fragmentation. ... 

FIGURE 7.6 Schematic of a laser-induced fluorescence detector. A lamp with focusing optics and an appropriate band-pass filter could be used in place of the laser excitation when tightly collimated light is not required. The emitted fluorescence is detected by a PMT that can be operated in current mode or photon counting mode. Inset shows the mutually perpendicular arrangement of excitation, capillary, and detection optics. 

Photofragmentation-laser-induced fluorescence (PD-LIF). This spectroscopic method is based on the photofragmentation of NH-, in a two-photon process using 193-nm radiation, followed by laser-induced fluorescence of the NH fragment (Schendel et al., 1990). The processes are as follows ... 

Tunable laser spectroscopic techniques such as laser-induced fluorescence (LIF) or resonantly enhanced multi-photon ionization (REMPI) are well-established mature fields in gas-phase spectroscopy and dynamics, and their application to gas-surface dynamics parallels their use elsewhere. The advantage of these techniques is that they can provide exceedingly sensitive detection, perhaps more so than mass spectrometers. In addition, they are detectors of individual quantum states and hence can measure nascent internal state population distributions produced via the gas-surface dynamics. The disadvantage of these techniques is that they are not completely general. Only some interesting molecules have spectroscopy amenable to be detected sensitively in this fashion, e.g., H2, N2, NO, CO, etc. Other interesting molecules, e.g. 02, CH4, etc., do not have suitable spectroscopy. However, when applicable, the laser spectroscopic techniques are very powerful. 

Miller et al. (8) report the CN(X E ) nascent vibrational populations detected by laser induced fluorescence after flash photolysis of C2N2 under collisionless conditions at 164, 158, and 154 nm. They report only the ratio of the CN(X2Z+, v = 1) to CN(X2E+, v = 0) populations. In all cases, they find this ratio to be less than 1, but increasing with higher photon energy. 

A much clearer picture evolves when one decomposes the total spectrum into the partial photodissociation cross sections a(, n,j) for absorbing a photon with wavelength A and producing NO in a particular vibrational-rotational state with quantum numbers (n,j). Experimentally this is accomplished by measuring so-called photofragment yield spectra. The idea is, in principle, simple the NO product is probed by laser-induced fluorescence (LIF). However, instead of scanning the wavelength Alif of the probe laser (in order to determine the final rotational state distribution) one fixes Alif to a particular transition NO(2n, nj) —>... 

All the techniques already developed for photodissociation dynamics can be used here (laser-induced fluorescence, time resolved spectroscopy, multi photon spectroscopy, etc). 

Laser-induced fluorescence (LIF) depends on the absorption of a photon to a real molecular state, and is therefore a much more sensitive technique, capable of detection of sub-part-per-billion concentrations. Thus, this is the most suitable for measurement of those minor species which are the transient intermediates in the reaction network. Here a tunable laser is required, as well as an electronic absorption system falling in an appropriate wavelength region serendipitously, many of the important transient species have band systems which are suitably located for application of LIF probing. The ability to sensitively detect transitions originating from electronically as well as vibrationally excited levels of a number of molecules offers the possibility of inquiring into the participation of non-equilibrium chemistry in combustion processes. 

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...

---