Matrix isolation fluorescence spectra

At low enough temperatures vibrational fine structure of aromatic chromophores may be well resolved, especially if they are embedded in a suitable matrix such as argon or N2, which is deposited on a transparent surface at 15 K. This matrix isolation spectroscopy77166 may reveal differences in spectra of conformers or, as in Fig. 23-16, of tautomers. In the latter example the IR spectra of the well-known amino-oxo and amino-hydroxy tautomers of cytosine can both be seen in the matrix isolation IR spectrum. Figure 23-16 is an IR spectrum, but at low temperatures electronic absorption spectra may display sharp vibrational structure. For example, aromatic hydrocarbons dissolved in n-heptane or n-octane and frozen often have absorption spectra, and therefore fluorescence excitation spectra, which often consist of very narrow lines. A laser can be tuned to excite only one line in the absorption spectrum. For example, in the spectrum of the carcinogen ll-methylbenz(a)anthrene in frozen octane three major transitions arise because there are three different environments for the molecule. Excitation of these lines separately yields distinctly different emission spectra.77 Likewise, in complex mixtures of different hydrocarbons emission can be excited from each one at will and can be used for estimation of amounts. Other related methods of energy-... 

Raman spectra of S2 in its triplet ground state have been recorded both in sulfur vapor and after matrix isolation using various noble gases. The stretching mode was observed at 715 cm in the gas phase [46], and at 716 cm in an argon matrix [71]. From UV absorption and fluorescence spectra of sulfur vapor the harmonic fundamental mode of the S2 ground state was derived as t e = 726 cm . The value corrected for anharmonicity is 720 cm [26, 27]. Earlier reports on the infrared absorption spectrum of 2 in matrix isolated sulfur vapor [72] are in error the observed bands at 660, 668 and 680 cm are due to S4 [17] and other species [73]. 

The different techniques of flash photolysis are used to detect transient species, that is atoms, molecules and fragments of molecules which have very short lifetimes. These cannot be observed by usual experimental techniques which require rather long observation times. For example, the measurement of an absorption or fluorescence spectrum takes several seconds, and this is of course far too long in the case of transient species which exist only for fractions of a second. In some cases these transient species can be stabilized through inclusion in low-temperature rigid matrices, a process known as matrix isolation . 

Figure 6.8. Fluorescence excitation spectra of matrix isolated 9-deuteroxyphenalenone (lower) and methyl-9-deuteroxyphenalenone (upper) as examples of nearly symmetric and asymmetric double well potentials for hydrogen transfer, shown on the left. The suppression of hot band 01 is shown in a separate spectrum at 3.5 K. Due to asymmetry of the potential, the wave functions are linear combinations of the left and right well function with different amplitudes if/t = a2 + b2, ij/a = -b2 + a2, b/a = 0.22 and 0.80 in the ground and excited states of the methyl derivative. (From Barbara et al. [1989].)...

Figure 3. Resonance Raman and fluorescence spectra of V isolated in solid Ar matrix (15 K) for different exciting laser lines for a matrix with V/Ar 2 y. 10 spectral slits 4 cm laser power at the sample was 20 mW for the 6348-nm line and 5 mW for all others. Key a, ground state resonance Raman spectrum b, excited state resonance Raman spectrum c, electronic resonance...

---