Fluorescence in supersonic jets

Lin CH, Fukii H, Imasaka T, et al. 1991. Synchronous scan luminescence techniques monitoring resonance and non-resonance fluorescence in supersonic jet spectrometry applied to anthracene derivatives. Anal Chem 63(14) 1433-1440. 

Electronic transitions in molecules in supersonic jets may be investigated by intersecting the jet with a tunable dye laser in the region of molecular flow and observing the total fluorescence intensity. As the laser is tuned across the absorption band system a fluorescence excitation spectrum results which strongly resembles the absorption spectrum. The spectrum... 

Although this book is devoted to molecular fluorescence in condensed phases, it is worth mentioning the relevance of fluorescence spectroscopy in supersonic jets (Ito et al., 1988). A gas expanded through an orifice from a high-pressure region into a vacuum is cooled by the well-known Joule-Thomson effect. During expansion, collisions between the gas molecules lead to a dramatic decrease in their translational velocities. Translational temperatures of 1 K or less can be attained in this way. The supersonic jet technique is an alternative low-temperature approach to the solid-phase methods described in Section 3.5.2 all of them have a common aim of improving the spectral resolution. 

The activated internal conversion, which is a hallmark of the photoexcited DNA bases, also occurs in a number of aromatic ethynes and nitriles, including dipheny-lacetylene (DPA) and 4-(dimethylamino)benzonitrile (DMABN). Thus, as in the case of the nucleobases, DPA exhibits an abrupt break-off (loss) of fluorescence in supersonic free jet [35], Figure 15-16, and the strong thermal quenching of... 

Several of these compounds have been studied without surrounding solvent in isolated gas phase conditions (supersonic jet studies) but evidence for TICT emission was found only in a few cases. More successful in terms of dual fluorescence in the jet were studies with respect to microsolvation and selfcluster formation. Both these processes enhance TICT formation. A beautiful example how pretwisting and microsolvation enhance the possibility for TICT formation is shown for a derivative of TriMAPYM in Fig. 4 [36],... 

Fig. 4. An ortho-methyl group in diethylamino-pyrimidin induces some ground state twist and hence energetically destabilizes the B state but not yet sufficiently to make the population of the A state a najor process in supersonic jet spectroscopy. Upper panel dispersed fluorescence spectra of the jet-cooled bare molecule [36]. In clusters with methanol, the TICT state is preferentially lowered, and the majority of the ob rved red-shifted fluorescence can be assign l to arise from the TICT state (lower panel). This does not occur for the compound without an ortho-methyl group.

A number of less commonly used analytical techniques are available for determining PAHs. These include synchronous luminescence spectroscopy (SLS), resonant (R)/nonresonant (NR)-synchronous scan luminescence (SSL) spectrometry, room temperature phosphorescence (RTP), ultraviolet-resonance Raman spectroscopy (UV-RRS), x-ray excited optical luminescence spectroscopy (XEOL), laser-induced molecular fluorescence (LIMP), supersonic jet/laser induced fluorescence (SSJ/LIF), low- temperature fluorescence spectroscopy (LTFS), high-resolution low-temperature spectrofluorometry, low-temperature molecular luminescence spectrometry (LT-MLS), and supersonic jet spectroscopy/capillary supercritical fluid chromatography (SJS/SFC) Asher 1984 Garrigues and Ewald 1987 Goates et al. 1989 Jones et al. 1988 Lai et al. 1990 Lamotte et al. 1985 Lin et al. 1991 Popl et al. 1975 Richardson and Ando 1977 Saber et al. 1991 Vo-Dinh et al. 1984 Vo- Dinh and Abbott 1984 Vo-Dinh 1981 Woo et al. 1980). More recent methods for the determination of PAHs in environmental samples include GC-MS with stable isotope dilution calibration (Bushby et al. 1993), capillary electrophoresis with UV-laser excited fluorescence detection (Nie et al. 1993), and laser desorption laser photoionization time-of-flight mass spectrometry of direct determination of PAH in solid waste matrices (Dale et al. 1993). 

Later workers accepted Porter s assignment without reservation [88], The gas phase spectrum was reproduced by Berry using phenyl azide as the precursor [25]. Laser-induced fluorescence attributed to triplet phenyl nitrene was observed upon pumping the 368 nm transition in ordinary gas phase experiments and in supersonic jet expansions where very highly resolved spectra could be generated [89a]. 

It is generally believed that among the pyrimidine bases, uracil and thymine mainly exist in the keto form. However, the existence of a small amount of the enol form of these compounds has also been indicated in some experiments. Hauswirth and Daniels have explained the observed deviation in the excitation spectrum of thymine firom the corresponding absorption spectrum in terms of the possibility of emission firom the enol tautomer. On the other hand, Vigny and Duquesne observed that both absorption and fluorescence excitation spectra of thymine are in resemblance with each other. Suwaiyan et al. have suggested the existence of a small amount of the enol tautomer in aqueous solutions of 5-chlorouracil at room temperature. The existence of keto-enol tautomerism in uracil, thymine and their derivatives has also been suggested in supersonic jet-cooled spectroscopic studies. ... 

Figure 7.10 Fluorescence excitation spectra of naphthalene (a) in room-temperature vapor at 5 X 10" torr (b) in supersonic jet, 0.07-torr hydrocarbon in 4 atm helium. The 8(b,g)J peak in the jet spectrum extends considerably offscale. Used with permission from S. Behlen, D. McDonald, V. Sethuraman, and S. A Rice J. C/ em. A /7y5. 75 5685 (1981).

Under conditions of moderate resolution, the spectrum in the region of the singlet-singlet system origin is diffuse and structureless. As the molecule does not fluoresce strongly, supersonic jet spectroscopy may not be possible for this system. 

In a skimmed supersonic jet, the parallel nature of the resulting beam opens up the possibility of observing spectra with sub-Doppler resolution in which the line width due to Doppler broadening (see Section 2.3.4) is reduced. This is achieved by observing the specttum in a direction perpendicular to that of the beam. The molecules in the beam have zero velocity in the direction of observation and the Doppler broadening is reduced substantially. Fluorescence excitation spectra can be obtained with sub-Doppler rotational line widths by directing the laser perpendicular to the beam. The Doppler broadening is not removed completely because both the laser beam and the supersonic beam are not quite parallel. 

The fluorescence excifafion spectra in Figures 9.47(a) and 9.47(b) show the Ojj bands of the A B2 X Ai system of aniline (see Figure 5.19) and the aniline Ar complex in a skimmed supersonic jet of aniline seeded into the argon carrier gas. 

Fluorescence excitation spectra of fairly large molecules in a supersonic jet are simplified, vibrationally, due to depopulation of low-lying vibrational levels in the ground electronic... 

Figure 9.48 Part of the fluorescence excitation spectrum of 1,2,4,5-tetrafluorobenzene in a supersonic jet. (Reproduced, with permission, from Okuyama, K., Kakinuma, T, Fujii, M., Mikami, N. and Ito, M., J. Phys. Chem., 90, 3948, f986)...

In a supersonic jet, the fluorescence spectra are virtually free of environmental perturbations (in contrast to condensed-phase samples) and can thus provide information on isolated solute molecules. Moreover, van der Waals complexes with other solute molecules can be studied, which is of great fundamental interest. 

Fluorescence-excitation, hole-burning, and dispersed-fluorescence spectra of 2,2 -bithiophene in a supersonic jet were measured (94JPC12893). 

Fuke and Kaya [1989] studied the tautomerization of dimer (6.15) formed in a supersonic jet to investigate the vibrational selectivity of concerted two-proton transfer in excited electronic state. Tunneling in the NH N fragments leads to broadening of certain vibrational bands in the fluorescence excitation spectrum (Figure 6.16). Tunneling is promoted by the symmetric intermolecular vibration with frequency 120 cm-1. The widths of bands with n = 0, 1, and 2 are 5, 10, and... 

Other techniques that have been used to determine polycyclic aromatic hydrocarbons in soil extracts include ELISA field screening [86], micellar elec-tr okinetic capillary chromatography [ 87], supersonic jet laser-induced fluorescence [88,89], fluorescence quenching [90], thermal desorption gas chromatography-mass spectrometry [81,90,100], microwave-assisted extraction [91], thermal desorption [92], immunochemical methods [93,94], electrophoresis [96], thin layer chromatography [95], and pyrolysis gas chromatography [35]. 

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