Lasers excitation

There is a large volume of contemporary literature dealing with the structure and chemical properties of species adsorbed at the solid-solution interface, making use of various spectroscopic and laser excitation techniques. Much of it is phenomenologically oriented and does not contribute in any clear way to the surface chemistry of the system included are many studies aimed at the eventual achievement of solar energy conversion. What follows here is a summary of a small fraction of this literature, consisting of references which are representative and which also yield some specific information about the adsorbed state. 

Pastirk I, Brown E J, Grimberg B I, Lozovoy V V and Dantus M 1999 Sequences for controlling laser excitation with femtosecond three-pulse four-wave mixing Faraday Discuss. 113 401... 

However, with the advent of lasers, the teclmique of laser-induced fluorescence (LIF) has probably become the single most popular means of detennining product-state distributions an early example is the work by Zare and co-workers on Ba + FLT (X= F, Cl, Br, I) reactions [25]. Here, a tunable laser excites an electronic transition of one of the products (the BaX product in this example), and the total fluorescence is detected as a... 

Figure A3.13.2 illustrates the origin of these quantities. Refer to [47] for a detailed mathematical discussion as well as the treatment of radiative laser excitation, in which incubation phenomena are unportant. Also refer to [11] for some classical examples in thennal systems.

Quack M 1991 Mode selective vibrational redistribution and unimolecular reactions during and after IR-laser excitation Mode Selective Chemistry ed J Jortner, R D Levine and B Pullman (Dordrecht Kluwer) pp 47-65... 

Ti sapphire laser excitation Chem. Phys. Lett. 233 519-24... 

Figure Bl.16.18. TREPR spectra observed after laser excitation of tetraphenylhydrazine in an SDS micelle at room temperature. Reprinted from [61].

Figure Bl.16.20. FTEPR spectra of photogenerated DQ m TXlOO solution for delay times between laser excitation of ZnTPPS and microwave pulse ranging from 20 ns to 11 ps. The central hyperfme line (M= 0) is at s - 4.5 MHz. Reprinted from [63].

This teclnhque can be used both to pennit the spectroscopic detection of molecules, such as H2 and HCl, whose first electronic transition lies in the vacuum ultraviolet spectral region, for which laser excitation is possible but inconvenient [ ], or molecules such as CH that do not fluoresce. With 2-photon excitation, the required wavelengdis are in the ultraviolet, conveniently generated by frequency-doubled dye lasers, rather than 1-photon excitation in the vacuum ultraviolet. Figure B2.3.17 displays 2 + 1 REMPI spectra of the HCl and DCl products, both in their v = 0 vibrational levels, from the Cl + (CHg) CD reaction [ ]. For some electronic states of HCl/DCl, both parent and fragment ions are produced, and the spectrum in figure B2.3.17 for the DCl product was recorded by monitoring mass 2 (D ions. In this case, both isotopomers (D Cl and D Cl) are detected. 

NH in its v = 1 vibrational level and in a high rotational level (e.g. J> 30) prepared by laser excitation of vibrationally cold NH in v = 0 having high J (due to nahiral Boltzmann populations), see figure B3.T3 and... 

The data obtained in tlie infrared-diode-laser-probe studies described above provides quenching infonnation at a given substrate donor energy E. By varying tlie laser excitation wavelengtli for production of vibrationally hot... 

Grabiner F R, Flynn G W and Ronn A M 1973 Vibration-vibration equilibration in laser excited CH3F and CH3F-X mixtures J. Chem. Phys. 59 2330-4... 

Emission spectroscopy is confined largely to the visible and ultraviolet regions, where spectra may be produced in an arc or discharge or by laser excitation. Absorption spectroscopy is, generally speaking, a more frequently used technique in all regions of the spectrum and it is for this reason that we shall concentrate rather more on absorption. 

Fig. 2. Raman spectra (T = 300 K) from various sp carbons using Ar-ion laser excitation (a) highly ordered pyrolytic graphite (HOPG), (b) boron-doped pyrolytic graphite (BHOPG), (c) carbon nanoparticles (dia. 20 nm) derived from the pyrolysis of benzene and graphitized at 2820°C, (d) as-synthesized carbon nanoparticles ( 850°C), (e) glassy carbon (after ref. [24]).

Kastner et al. [25] also reported Raman spectra of cathode core material containing nested tubules. The spectral features were all identified with tubules, including weak D-band scattering for which the laser excitation frequency dependence was studied. The authors attribute some of the D-band scattering to curvature in the tube walls. As discussed above, Bacsa et al. [26] reported recently the results of Raman studies on oxidatively purified tubes. Their spectrum is similar to that of Hiura et al. [23], in that it shows very weak D-band scattering. Values for the frequencies of all the first- and second-order Raman features reported for these nested tubule studies are also collected in Table 1. 

In the following sections, we first show the phonon dispersion relation of CNTs, and then the calculated results for the Raman intensity of a CNT are shown as a function of the polarisation direction. We also show the Raman calculation for a finite length of CNT, which is relevant to the intermediate frequency region. The enhancement of the Raman intensity is observed as a function of laser frequency when the laser excitation frequency is close to a frequency of high optical absorption, and this effect is called the resonant Raman effect. The observed Raman spectra of SWCNTs show resonant-Raman effects [5, 8], which will be given in the last section. 

Quantum effects are observed in the Raman spectra of SWCNTs through the resonant Raman enhancement process, which is seen experimentally by measuring the Raman spectra at a number of laser excitation energies. Resonant enhancement in the Raman scattering intensity from CNTs occurs when the laser excitation energy corresponds to an electronic transition between the sharp features (i.e., (E - ,)" type singularities at energy ,) in the ID electronic DOS of the valence and conduction bands of the carbon CNT. 

Since the separation energies between these sharp features in the 1D DOS are strongly dependent on the CNT diameter, a change in the laser excitation energy may bring into optical resonance a CNT with a different diameter. However,... 

Morishima et al. [75, 76] have shown a remarkable effect of the polyelectrolyte surface potential on photoinduced ET in the laser photolysis of APh-x (8) and QPh-x (12) with viologens as electron acceptors. Decay profiles for the SPV (14) radical anion (SPV- ) generated by the photoinduced ET following a 347.1-nm laser excitation were monitored at 602 nm (Fig. 13) [75], For APh-9, the SPV- transient absorption persisted for several hundred microseconds after the laser pulse. The second-order rate constant (kb) for the back ET from SPV- to the oxidized Phen residue (Phen+) was estimated to be 8.7 x 107 M 1 s-1 for the APh-9-SPV system. For the monomer model system (AM(15)-SPV), on the other hand, kb was 2.8 x 109 M-1 s-1. This marked retardation of the back ET in the APh-9-SPV system is attributed to the electrostatic repulsion of SPV- by the electric field on the molecular surface of APh-9. The addition of NaCl decreases the electrostatic interaction. In fact, it increased the back ET rate. For example, at NaCl concentrations of 0.025 and 0.2 M, the value of kb increased to 2.5 x 108 and... 

It has been shown in Chapter 5, the fluorescence quenching of the DPA moiety by MV2 + is very efficient in an alkaline solution [60]. On the other hand, Delaire et al. [124] showed that the quenching in an acidic solution (pH 1.5-3.0) was less effective (kq = 2.5 x 109 M 1 s 1) i.e., it was slower than the diffusion-controlled limit. They interpreted this finding as due to the reduced accessibility of the quencher to the DPA group located in the hydrophobic domain of protonated PMA at acidic pH. An important observation is that, in a basic medium, laser excitation of the PMAvDPA-MV2 + system yielded no transient absorption. This implies that a rapid back ET occurs after very efficient fluorescence quenching. 

In general, the choice of a laser for use as a Raman excitation source is based on a number of considerations. The laser excitation wavelength, for experimental and theoretical reasons, must lie in the visible region, i.e. 400-700 nm. The laser should have many emission lines over a wide range of the visible region and the excitation frequency should not correspond... 

Reactions that proceed photochemically do not necessarily involve observations of an excited state. Long before observations are made, the excited state may have dissociated to other fragments, such as free radicals. That is, the lifetime of many excited states is shorter than the laser excitation pulse. This statement was implied, for example, by reactions (11-46) and (11-47). In these systems one can explore the kinetics of the subsequent reactions of iodine atoms and of Mn(CO)s, a 17-electron radical. For instance, one can study... 

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