Highly resolved emission data

The model system generally uses EMEP emissions. For the countries - Austria, Czech Republic, Slovakia and Hungary - the original 50 x 50 km data are down-scaled to 5 X 5 km based on an inventory from 1995 (Winiwarter and Zueger 1996). The EMEP data for 1999 (used for 2005 forecast) have been substituted by data for 2003 (Vestreng et al. 2004). In addition, a new highly resolved emission inventory for the city of Vienna, Austria (Orthofer et al. 2005) is used for this area. 

In addition to the ODMR investigations of Rh +(4d )-chelates, recently similar studies have been performed for the Pd +(4d )-complexes, Pd(thpy)2 and Pd(qol)2 (with qol" = 8-hydroxyquinolinate) [80, 81]. Optical investigations of Pd(thpy)2 (with (thpy) 2,2 -thienylpyridinate, see Fig. 1) doped into an n-oc-tane Shpol skii matrix revealed highly resolved emission spectra and showed that the phosphorescent triplet state decays with three hfetime components of T] = 1200 ps, T]] = 235 ps, and rm = 130 ps characteristic of the triplet state sub-levels [82 - 84]. The emission data of Pd(qol)2 in an n-octane ShpoTskii matrix have been reported recently [81,85]. Two distinct emissive sites in the matrix were found,with electronic origins at 16,090 cm (77%) and 16,167 cm (23%), respectively. From the Zeeman splittings of the optical hne transitions in magnetic fields up to 12 T, the emission for the two sites was assigned as Tj Sg. 

Fig. 8 Thermalized emission decay time of site A of Ir(4,6-dFppy)2(acac) in CH2C12 vs temperature. The emission was detected at the energy of the 0-0 transition I — 0 at 21,025 cm-1. The solid line represents a fit of (2) to the experimental data. The fit was performed with fixed values for AEU1 and AEm v which are known from highly resolved spectra (see above). The results obtained from the fit are shown in the inset (compare [50])...

Table 3 summarizes all matrices for which highly resolved spectra have been obtained, and gives a number of photophysical data found for the [Rulbpylj] chromophores (transition energies, zero-field splittings, emission lifetimes). Interestingly, the transition energy from the ground state to the lowest triplet sublevel ] I) varies over more than 200 cm, which may be used in the sense of chemical tunability . 

In chloroform solvent, the platinum dithiolene complexes Pt(S2C2R2)2 are photooxidized between 300 and 350 nm, providing the complexes used are those for which the R groups result in redox potentials in the 0.1 to 0.5 V (vs SCE) range. The results are consistent with the reaction shown in equation (534).1849 Further work on this system identifies the fact that several excited states are probably photoreactive in this process,1850 and no definitive answer on the excited state reactivities is yet available. Very recently, however, highly structured solid-state emissions have been observed for Pt S2C2(CN)2 P(OR)3 2, and this data may help resolve some of these questions.1851... 

The experimental data shown in Figs. 15.3 and 15.5 were obtained with a microwave frequency oj/2ji > lit where r is the time or duration of the collision and 1/r is the linewidth. In this case the resonances corresponding to the absorption or emission of different numbers of photons are resolved. Here we describe radiative collisions starting from the high frequency regime, oj/2ji > 1/r and progressing to the low frequency regime, a> 2n < 1/r. 

---