Multi-photon

The temi action spectroscopy refers to those teclmiques that do not directly measure die absorption, but rather the consequence of photoabsorption. That is, there is some measurable change associated with the absorption process. There are several well known examples, such as photoionization spectroscopy [47], multi-photon ionization spectroscopy [48], photoacoustic spectroscopy [49], photoelectron spectroscopy [, 51], vibrational predissociation spectroscopy [ ] and optothemial spectroscopy [53, M]. These teclmiques have all been applied to vibrational spectroscopy, but only the last one will be discussed here. 

The Goeppert-Mayer two- (or multi-) photon absorption, mechanism (ii), may look similar, but it involves intennediate levels far from resonance with one-photon absorption. A third, quasi-resonant stepwise mechanism (iii), proceeds via smgle- photon excitation steps involvmg near-resonant intennediate levels. Finally, in mechanism (iv), there is the stepwise multiphoton absorption of incoherent radiation from themial light sources or broad-band statistical multimode lasers. In principle, all of these processes and their combinations play a role in the multiphoton excitation of atoms and molecules, but one can broadly... 

Quack M 1998 Multi photon excitation Encyclopedia of Computational Chemistry o 3, ed P v R Schleyer et al (New York Wiley) pp 1775-91... 

Laser Ionization Mass Spectrometry Laser Microprobe Mass Analysis Laser Microprobe Mass Spectrometry Laser Ionization Mass Analysis Nonresonant Multi-Photon Ionization... 

Surface Analysis by Laser Ionization Post-Ionization Secondary Ion Mass Spectrometry Multi-Photon Nonresonant Post Ionization Multiphoton Resonant Post Ionization Resonant Post Ionization Multi-Photon Ionization Single-Photon Ionization... 

Theoretical predictions must be compared to appropriate high quality experimental results. Allowed transitions (having oscillator strength greater than 0) may be compared to standard one-photon spectroscopic data. However, forbidden transitions must be compared to multi-photon experiments, and both types must be considered before a complete characterization of a system s excited states can be made. 

Multi-photon processes involve higher Fourier components of the electron density. For example, the density fluctuation caused by two photons with frequencies and ui2 can be described by =... 

The NIR femtosecond laser microscope realized higher order multi photon excitation for aromatic compounds interferometric autocorrelation detection of the fluorescence from the microcrystals of the aromatic molecules confirmed that their excited states were produced not via stepwise multiphoton absorption but by simultaneous absorption of several photons. The microscope enabled us to obtain three-dimensional multiphoton fluorescence images with higher spatial resolution than that limited by the diffraction theory for one-photon excitation. 

Photoionization ti me-of-fli ght mass spectrometry is almost exclusively the method used in chemical reaction studies. The mass spectrometers, detectors and electronics are almost identical. A major distinction is the choice of ionizing frequency and intensity. For many stable molecules multi photon ionization allowed for almost unit detection efficiency with controllable fragmentation(20). For cluster systems this has been more difficult because high laser intensities generally cause extensive dissociation of neutrals and ions(21). This has forced the use of single photon ionization. This works very well for low i oni zati on potential metals ( < 7.87 eV) if the intensity is kept fairly low. In fact for most systems the ionizing laser must be attenuated. A few very small... 

Barber, P. R., Ameer-Beg, S. M., Gilbey, J. D., Edens, R. J., Ezike, I. and Vojnovic, B. (2005). Global and pixel kinetic data analysis for FRET detection by multi-photon time-domain FLIM. In Multiphoton Microscopy in the Biomedical Sciences V.Vol. 5700. SPIE, San Jose, CA, USA, pp. 171-81. 

Deguil, N., Mottay, E., Salin, F., Legros, P. and Choquet, D. (2004). Novel diode-pumped infrared tunable laser system for multi-photon microscopy. Microsc. Res. Tech. 63, 23-6. 

The total fluorescence intensity saturated around a few hundreds of mJ/cm2 which corresponds to the irradiation condition where the new plasma-like emission was observed. Above this value fluorescence intensity decreased, which is accompanied with the recovery of the relative intensity of excimer emissions. This means that a quite efficient deactivation channel of excitation intensity opens in this energy range, and the contribution of Si -Si annihilation is depressed. This suggests that fragmentation reactions to diatomic radicals are not induced by the annihilation process. Multi-photon absorption processes via the Si states and chemical intermediates should be involved, although no direct experimental result has as yet been obtained. 

One attractive possibility is to develop CPs that can be used for in vivo imaging of protein aggregates. In this regard, the synthesis of appropriately functionalized CPs that are able to cross the blood-brain barrier (BBB) has been exemplified [36]. Such dyes can be utilized in powerful multi-photon imaging applications as previously reported CPs have been shown to have an excellent cross-section area compared with small fluorescent dyes, making these molecules suitable for multiphoton applications [33, 37]. 

Uranium enrichment using LIS has been exhaustively studied and the conceptual outlines of two different methods can be found in the open literature. These methods are multi-photon dissociation of UF6 (SILEX, or Separation of Isotopes by Laser Excitation) and laser excitation of monatomic uranium vapor (Atomic Vapor Laser Isotope Separation, or AVLIS). Following an enormous investment, AVLIS was used by the United States DOE in the 1980s and early 1990s, but due to the present oversupply of separated uranium, the plant has been shut down. 

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. ... 

Photoionization, where electrons are released by molecules following the absorption of energy from photons, has long been viewed as a non-radioactive means to ionize explosives in the vapor phase [39]. In recent years, two teams have sought to employ laser ionization with IMS for explosive determinations. A team at Implant Sciences Corporation has utilized a laser (or flash lamp) for sampling surfaces and for ionization of sample vapors in an IMS analyzer [40, 41]. In their approach, the sample is removed from a surface with an increased temperature from laser exposure. Gases (and presumably particulate matter) from over the surface are drawn into an IMS drift tube using a wall-free inlet vida supra). In the IMS drift tube, resonance multi-photon ionization by a laser is used to produce ions from the explosives. Their... 

Many other applications of multi-photon absorption spectroscopy have meanwhile been reported in photochemistry and also in solid state physics, for instance, a new assignment of the band gap in alkali bromides by Froehlich et al Some further examples will be discussed in Section 111.10). 

Spiropyran and the related compounds all undergo interesting photo-transformation in the crystalline state. There are examples of all these compounds undergoing both multi-photon- and single-photon-induced transformations in the crystalline state [77,106-110]. 

FIGURE 2.1 A diagram of a multi-photon microscope. For AF, SFIG and exogenous probe fluorescence only one laser is used. The fluorescence or SHG signal passes through a dichroic mirror to the detector(s). One or two detectors and the appropriate filters can be used to collect multiple emission signals simultaneously. A spectrometer can be placed in the detector path to collect spectra, or a polarizer can be used to collect polarization data. 

Kawata, Y, Xu, C., and Denk, W. 1999. Feasibility of molecular-resolution fluorescence nearfield microscopy using multi-photon absorption and field enhancement near a sharp tip. J. Appl. Phys. 85 1294-1301. 

Organic-silica hybrid materials have been used for multi-photon microfabrication. These include the acrylate-functionalized oligosiloxanes known as ORMOCERs, which have been polymerized by radical processes using conventional IP radical iniatitors, such as c.2 [221,234]. Commercial poly(dimethylsiloxane)-based resists containing vinyl and Si-H functionalities use two different 2PA-induced processes hydrosilylation catalyzed by the photodecomposition products of Cp PtMes (Cp = ti -methylcyclopentadienyl) and radical initiation by c.4 (Fig. 13) [235]. The former process was complicated by thermally-induced polymerization. 

Baldeck and Andraud provide a chapter entitled Exitonic Coupled Oligomers and Dendrimers for Two-Photon Absorption, wherein the concepts of exci-tonic coupling are developed and their relevance to multi-photon absorption processes are described. 

MDGC, and comprehensive two-dimensional GC, or GCxGC), faster separation techniques (fast GG), fast methods for quality assessment or process control in the flavour area ( electronic noses and fingerprinting MS) and on-line time-resolved methods for analysis of volatile organic compounds (VOGs) such as proton-transfer reaction MS (PTR-MS) and resonance-enhanced multi-photon ionisation coupled with time-of-flight MS (REMPI-TOFMS). The scope of this contribution does not allow for lengthy discussions on all available techniques therefore, only a selection of developments will be described. 

REMPI Resonantly Enhanced Multi-Photon Ionization... 

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. 

Control of nonlinear optical excitation with multi photon inirapnlsc interference... 

S. Kielich. Multi-photon scattering molecular spectroscopy. Prog. Optics, 20 155, 1983. 

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