Time-resolved spectroscopies CARS

Suggestive evidence for the protonation of diphenylcarbene was uncovered in 1963.10 Photolysis of diphenyldiazomethane in a methanolic solution of lithium azide produced benzhydryl methyl ether and benzhydryl azide in virtually the same ratio as that obtained by solvolysis of benzhydryl chloride. These results pointed to the diphenylcarbenium ion as an intermediate in the reaction of diphenylcarbene with methanol (Scheme 3). However, many researchers preferred to explain the O-H insertion reactions of diarylcarbenes in terms of electrophilic attack at oxygen (ylide mechanism),11 until the intervention of car-bocations was demonstrated by time-resolved spectroscopy (see Section III).12... 

The study of photochromic materials is an active area of research. Picosecond time resolved spectroscopy has been used to investigate primary processes in ring opening in the photochromism of spiroxazines . CARS has also been used to investigate solvent effects on isomeric distributions in the same systerns. ... 

Recently, the femtosecond time-resolved spectroscopy has been developed and many interesting publications can now be found in the literature. On the other hand, reports on time-resolved vibrational spectroscopy on semiconductor nanostructures, especially on quantum wires and quantum dots, are rather rare until now. This is mainly caused by the poor signal-to-noise ratio in these systems as well as by the fast decay rates of the optical phonons, which afford very fast and sensitive detection systems. Because of these difficulties, the direct detection of the temporal evolution of Raman signals by Raman spectroscopy or CARS (coherent anti-Stokes Raman scattering) [266,268,271-273] is often not used, but indirect methods, in which the vibrational dynamics can be observed as a decaying modulation of the differential transmission in pump/probe experiments or of the transient four-wave mixing (TFWM) signal are used. 

Meyer S and Engel V 2000 Femtosecond time-resolved CARS and DFWM spectroscopy on gas-phase I, a ... 

Toleutaev B N, Tahara T and Hamaguchi H 1994 Broadband (1000 cm multiplex CARS spectroscopy application to polarization sensitive and time-resolved measurements Appl. Phys. 59 369-75... 

Several types of time-resolved Raman spectroscopies have been reported and reviewed by Hamaguchi and co-workers and Hamaguchi and Gustafson. These include pump-probe spontaneous and time-resolved coherent Raman spectroscopy of the anti-Stokes and Stokes varieties [coherent anti-Stokes Raman spectroscopy (CARS) and coherent Stokes Raman spectroscopy (CSRS)], respectively). Here we will focus on pump-probe time-resolved spontaneous Raman spectroscopy. 

The coherent fs time-resolved CARS method is highly sensitive for the investigation of collision induced (or pressure dependent) changes in optical line shapes especially when line mixing occurs and frequency resolved measurements come to their limits [7]. The fs-CARS spectroscopy is applied to various collision systems (N2-N2, N2-rare gas, C2H2-C2H2, CO-CO)... 

After the introduction of frequency resolved CARS by Maker and Terhune [1], time resolved experiments became possible with the invention of high power lasers with femtosecond resolution. Leonhardt [2] and for example Hayden [3] performed femtosecond CARS experiments in liquids. A first femtosecond time resolved CARS experiment in gas phase was performed by Motzkus et. al. [4] where the wave packet dynamics of the dissociation of Nal was monitored. The first observation of wave packet dynamics in gaseous iodine was reported by Schmitt et al. [5]. They were able to observe dynamics in both, the ground and excited state with the same experiment. A summary of high resolution spectroscopy in gas phase by nonlinear methods is given by Lang et al. [6]. 

Beyond imaging, CARS microscopy offers the possibility for spatially resolved vibrational spectroscopy [16], providing a wealth of chemical and physical structure information of molecular specimens inside a sub-femtoliter probe volume. As such, multiplex CARS microspectroscopy allows the chemical identification of molecules on the basis of their characteristic Raman spectra and the extraction of their physical properties, e.g., their thermodynamic state. In the time domain, time-resolved CARS microscopy allows recording of ultrafast Raman free induction decays (RFIDs). CARS correlation spectroscopy can probe three-dimensional diffusion dynamics with chemical selectivity. We next discuss the basic principles and exemplifying applications of the different CARS microspectroscopies. 

Table II Space- and Time-Resolved Measurements from Inelastic Light Scattering. All methods are suitable for nonequilibrium conditions. Here, RS refers to Raman scattering, CARS to coherent anti-Stokes Raman spectroscopy, and RIKES to Raman-induced Kerr effect.

In this chapter we will first discuss coherent anti-Stokes Raman scattering (CARS) of simple liquids and binary mixtures for the determination of vibrational dephasing and correlation times. The time constants represent detailed information on the intermolecular interactions in the liquid phase. In the second section we consider strongly associated liquids and summarize the results of time-resolved IR spectroscopy (see, e.g., Ref. 17) on the dynamics of monomeric and associated alcohols as well as isotopic water mixtures. 

The spectroscopic methods are based on time-resolved pump-probe schemes where the collision-free regime is usually attained by using low pressure conditions. Application of various linear and non-linear laser techniques, such as LIF (laser-induced fluorescence), REMPI (resonant-enhanced multiphoton ionization) and CARS (coherent antistokes Raman spectroscopy) have provided detailed information on the internal states of nascent reaction products [58]. Obviously, an essential prerequisite for the application of these techniques is the knowledge of the spectroscopic properties of the products. 

Several hetero-bischelated complexes of Ir(III) with 1,10-phenanthroline and substituted 1,10-phenanthroline have also been reported to have non-exponential luminescence decay curves (19). Although the individual emission spectra of the non-equilibrated levels of these complexes are again too close to resolve by conventional emission spectroscopy, partial resolution has been accomplished by time-resolved emission spectroscopy via box-car averaging techniques (20). Complete resolution has been accomplished by computer analysis of luminescence decay curves as a function of emission wavelength (20). In these complexes, the luminescent levels appear to arise from both ligand-localized ( tttt ) states and charge-transfer ( ) states. 

CARS has been successfully used for the spectroscopy of chemical reactions (Sect. 8.4). The BOX CARS technique with pulsed lasers offers spectral, spatial, and time-resolved investigations of collision processes and reactions, not only in laboratory experiments but also in the tougher surroundings of factories, in the reaction zone of car engines, and in atmospheric research (Sect. 10.2 and [380, 381]). 

Among approaches in vibrational spectroscopy are differential and time-resolved IR and Raman spectroscopy, coherent anti-Stokes Raman scattering (CARS), Fourier transform infrared spectroscopy (FT-IR) multidimensional IR and RR spectroscopy, two-dimensional infrared echo and Raman echo [56], and ultrafast time-resolved spontaneous and coherent Raman spectroscopy the structure and dynamics of photogenerated transient spedes [50, 57]. 

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