Spectrum resonance fluorescence

Beattie, I.R., Ozin, G.A., and Perry, R.O., Gas phase Raman spectra of P4, P2, As4 and As2. Resonance fluorescence spectrum of 80Se2. Resonance fluores-cence-Raman effects in the gas-phase spectra of sulfur and iodine. Effect of pressure on the depolarization ratios for iodine,. Chem. Soc., Perkin I, 2071, 1970. 

Other spectral regions are also important because the detection and quantification of small concentrations of labile molecular, free radical, and atomic species of tropospheric interest both in laboratory studies and in ambient air are based on a variety of spectroscopic techniques that cover a wide range of the electromagnetic spectrum. For example, the relevant region for infrared spectroscopy of stable molecules is generally from 500 to 4000 cm-1 (20-2.5 /Am), whereas the detection of atoms and free radicals by resonance fluorescence employs radiation down to 121.6 nm, the Lyman a line of the H atom. 

CIO and BrO abundances are detected simultaneously and continuously as the airstream passes through the instrument. They are not detected directly but are chemically converted to Cl and Br atoms by reaction with reagent nitric oxide gas that is added to the airstream inside the instrument. The Cl and Br atoms are then detected directly with resonance fluorescence in the 2D5/2 -> 2P3/2 transitions in the vacuum ultraviolet region of the spectrum. In resonance fluorescence, the emissions from the light sources are resonantly scattered off of the Cl and Br atoms in the airstream and are detected by a photomultiplier tube set at right angles to both the light source and the flow tube. The chemical conversion reactions... 

Figure 3.10 The electronic transitions [absorption in (a)] of small molecules show vibrational and rotational lines in addition to the purely electronic spectrum, (b) Luminescence emission is resonance fluorescence (f), and chemical reactions (R) can originate from several excited states...

Rotational Raman spectra of N2 and O2 Resonance fluorescence spectrum of Br2 Vibrational-rotational spectra of CD3H and CH3D Spectrophotometric study of stabihty of metal ion-EDTA complexes Kinetics of the H2 + I2 = 2HI reaction in the gas phase Weak-acid catalysis of BH4 decomposition Photochemistry of the cis-trans azobenzene interconversion Isotope effect on reaction-rate corrstants... 

The resonance Raman and resonance fluorescence contributions are seen separated in the closer look seen in Fig. 18.9. The observed spectrum is assigned to emission from the origin of the electronic excited state onto a particular vibronic level in the ground electronic state. For reasons irrelevant to our discussion the Raman line appears as a doublet in this high-resolution spectrum. The emission... 

Further support for this interpretation is given by the temperature dependence of the same emission spectrum shown in Fig. 18.10. At T = 4 K we see only the doublet that corresponds to the Raman scattering signal. As T increases this coherent peak is reduced, and intensity is growing in the broad resonance fluorescence peak... 

Continuum resonance-Raman scattering can be observed under discrete resonance-Raman scattering conditions only if the resonance fluorescence is quenched, either with an inert gas, or (in the case of condensed phase studies) by the solvent or matrix. Thus, on excitation of a liquid, solution, or solid within the contour of an absorption band, the Raman spectrum observed has the characteristics of the continuum rather than the discrete case or, in other terminology, of resonance Raman, rather than resonance fluorescence spectra. Such spectra provide unique information on the spectroscopic properties of radical cations and ions, some of which species are unstable in air. Particularly noteworthy have been the studies by Andrews et al. (65) which have... 

A considerable progress in this direction was achieved by investigating the fluorescence spectrum of ultra-cold atoms in an optical lattice in a heterodyne experiment (lessen et al. (3)). In these measurements a linewidth of 1 kHz was achieved, however, the quantum aspects of the resonance fluorescence such as antibunched photon statistics cannot be investigated under these conditions since they wash out when more than one atom is involved. 

In conclusion, we have presented the Hrst high-resolution heterodyne measurement of the elastic peak in resonance fluorescence of a single ion. At identical experimental parameters we have also measmed antibunching in the photon correlation of the scattered Held. Together, both measurements show that, in the limit of weak excitation, the fluorescence light differs from the excitation radiation in the second-order correlation but not in the first order correlation. However, the elastic component of resonance fluorescence combines an extremely narrow frequency spectrum with antibunched photon statistics, which means that the fluorescence radiation is not second-order coherent as expected from a classical point of view. This apparent contradiction can be explained easily by taking into accoimt the quantum nature of light, since first-order coherence does not imply second-order coherence for quantized fields (19). The heterodyne and the photon correlation measurement are complementary since they emphasize either the classical wave properties or the quantum properties of resonance fluorescence, respectively. 

UV spectra of pyridazines and pyridazinones were recorded, and solvent effects on spectra were examined. 644-652 The absorption spectrum of the pyridazine radical was reported.653 Resonance fluorescence has been observed from pyridazine vapor.654 Electron transmission spectroscopy has... 

Smalley and co-workers have probed intramolecular vibrational relaxation by viewing the yields and the time-dependence of the fluorescence from Sj in alkylated benzenes. They focus attention on those ring modes whose vibrational frequencies are unshifted by alkylation these are vibrations with nodes at the alkylated ring carbon atom. The absorption lines are sharp, but as the alkyl chain is lengthened, the emission spectrum develops a broad relaxed component, while the intensity of the sharp unrelaxed resonance fluorescence diminishes in intensity as the intensity of the relaxed spectrum increases. The time-dependence of the relaxed and unrelaxed emission is found to be a single exponential decay, so unfortunately, the rapid intramolecular dephasing decay has not yet been followed. 

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