Coherent anti-Stokes Raman spectroscop

The vibrational modes of clusters of water molecules were emphasized in a study up to the tetramer level ", motivated by IR and coherent anti-Stokes Raman spectroscopic data. Cal-... 

New metliods appear regularly. The principal challenges to the ingenuity of the spectroscopist are availability of appropriate radiation sources, absorption or distortion of the radiation by the windows and other components of the high-pressure cells, and small samples. Lasers and synchrotron radiation sources are especially valuable, and use of beryllium gaskets for diamond-anvil cells will open new applications. Impulse-stimulated Brillouin [75], coherent anti-Stokes Raman [76, 77], picosecond kinetics of shocked materials [78], visible circular and x-ray magnetic circular dicliroism [79, 80] and x-ray emission [72] are but a few recent spectroscopic developments in static and dynamic high-pressure research. 

In order to realize molecular-vibration spectroscopy, coherent anti-Stokes Raman scattering (CARS) spectroscopy is employed, which is one of the most widely used nonlinear Raman spectroscopes (Shen 1984). CARS spectroscopy uses three incident fields including a pump field (< i), a Stokes field (0)2, 0 2 < 1) and a probe field (<0/ = <0i), and induces a nonlinear polarization at the frequency of <03 = 2<0i - <02 which is given in a scalar form by... 

Here, E is the strength of the applied electric field (laser beam), a the polarizability and / and y the first and second hyper-polarizabilities, respectively. In the case of conventional Raman spectroscopy with CW lasers (E, 104 V cm-1), the contributions of the / and y terms to P are insignificant since a fi y. Their contributions become significant, however, when the sample is irradiated with extremely strong laser pulses ( 109 V cm-1) created by Q-switched ruby or Nd-YAG lasers (10-100 MW peak power). These giant pulses lead to novel spectroscopic phenomena such as the hyper-Raman effect, stimulated Raman effect, inverse Raman effect, coherent anti-Stokes Raman scattering (CARS), and photoacoustic Raman spectroscopy (PARS). Figure 3-40 shows transition schemes involved in each type of nonlinear Raman spectroscopy. (See Refs. 104-110.)... 

Michele Marrocco, PhD, is a researcher in laser spectroscopy at ENEA (Rome, Italy) (1999 to present). He received his degree in physics from the University of Rome in 1994. He was employed as a postdoctorate at the Max-Planck Institute for Quantum Optics (Munich, Germany), as a researcher at the Quantum Optics Labs at the University of Rome (Rome, Italy), and as an optics researcher by the army. His research activities include traditional and innovative spectroscopic techniques for diagnosis of combustion and nanoscopic systems studied by means of optical microscopy. The techniques used include adsorption, laser induced fluorescence, spontaneous Raman, stimulated Raman gain, stimulated Raman loss, coherent anti-Stokes Raman, degenerate four wave mixing, polarization spectroscopy, laser induced breakdown, laser induced incandescence, laser induced thermal gratings. He has over 30 technical publications. 

Coherent anti-Stokes Raman scattering, CARS, appears to be a promising spectroscopic method of investigating vibrationally excited intermediates formed in isomerization reactions of large polyatomic molecules. The state of cycloheptatriene and its 7-methyl derivative, formed by absorption at 266 nm. 

In addition to laser fluorescence excitation, several other laser spectroscopic methods have been found to be useful for the state-selective and sensitive detection of products of reactive collisions resonance-enhanced multiphoton ionization [58], coherent anti-Stokes Raman scattering [M], bolometric detection with laser excitation [30], and direct infrared absorption [7]. Several additional laser techniques have been developed for use in spectroscopic studies or for diagnostics in reacting systems. Of these, four-wave mixing [ ] is applicable to studies of reaction dynamics although it does have a somewhat lower sensitivity than the techniques mentioned above. 

In its broadest sense, spectroscopy is concerned with interactions between light and matter. Since light consists of electromagnetic waves, this chapter begins with classical and quantum mechanical treatments of molecules subjected to static (time-independent) electric fields. Our discussion identifies the molecular properties that control interactions with electric fields the electric multipole moments and the electric polarizability. Time-dependent electromagnetic waves are then described classically using vector and scalar potentials for the associated electric and magnetic fields E and B, and the classical Hamiltonian is obtained for a molecule in the presence of these potentials. Quantum mechanical time-dependent perturbation theory is finally used to extract probabilities of transitions between molecular states. This powerful formalism not only covers the full array of multipole interactions that can cause spectroscopic transitions, but also reveals the hierarchies of multiphoton transitions that can occur. This chapter thus establishes a framework for multiphoton spectroscopies (e.g., Raman spectroscopy and coherent anti-Stokes Raman spectroscopy, which are discussed in Chapters 10 and 11) as well as for the one-photon spectroscopies that are described in most of this book. 

NH2 detection with coherent anti-Stokes-Raman scattering (CARS) was reported in [48]. The author found spectroscopic and kinetic evidence for an NH2 CARS spectrum in the wavelength range 3195 to 3225 cm during laser photolysis of NH3 [48]. 

Coherent anti-Stokes Raman (CARS) scattering spectroscopy probes vibrational levels based on a coherent non-linear wave mixing process and is a powerful technique for the vibrational imaging of biological structures. Daniel L. Marks and Stephen A. Boppart discuss new pulse-shaping and interferometry schemes in CARS that improve its spectroscopic capability for biological applications. 

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