Bicyclopropylidene 1a and its octamethyl derivative 1b are subjected to ionization by X-irradiation in solid argon. In accord with previous experiments, this treatment leads to the spontaneous opening of both cyclopropylidene rings, as does ionization of 1b by gamma-irradiation in CFCl(3) at 77 K. The resulting tetramethyleneethane (or bisallyl) radical cations 2a+* and 2b+* are distinguished by a broad band in the NIR. In the case of 2a+*, wavelength-selective photolyses reveal the presence of two interconvertible species with very similar yet distinct spectra. Based on DFT and CASSCF/CASPT2 calculations, these spectra are assigned to two "electromeric" forms of 2a+* which differ in the nature of the singly occupied MO. The NIR bands correspond to charge-resonance transitions between states with fully delocalized spin and charge. Calculations predict that similar electromers should also exist in 2b+* which shows a much weaker NIR band, but no corresponding experimental evidence could be found. On the other hand, the ESR spectrum of 2b+* indicates that, in contrast to 2a+*, the spin is largely localized in one of the two allylic moieties in 2b+*. Although no theoretical method is presently available that would permit an accurate modeling of the opposing factors favoring localized or delocalized structures in molecules such as 2a+* or 2b+*, the observed trends can be satisfactorily rationalized on the basis of semiquantitative considerations. In particular, the important role of vibronic coupling in shaping the potential surfaces for such systems is emphasized.
, generated by radiolytic oxidation of the parent compound in argon and Freon matrices at low temperatures, undergoes a spontaneous rearrangement to form the distonic 1,1-dimethyleneallene (or 2-vinylideneallyl) radical cation 3•+ consisting of an allyl radical substituted at the 2-position by a vinyl cation. In similar matrix studies, it is found that the isomeric dimethylenecyclopropane radical cation 2•+ also rearranges to 3 •+ . The unusual molecular and electronic structure of 3•+ has been established by the results of ESR, UV-vis, and IR spectroscopic measurements in conjunction with detailed theoretical calculations. Also of particular interest is an NIR photoinduced reaction by which 3 •+ is cleanly converted to the vinylidenecyclopropane radical cation 4•+ , a process that can be represented in terms of a single electron transfer from the allyl radical to the vinyl cation followed by allyl cation cyclization. The specificity of this photochemical reaction provides additional strong chemical evidence for the structure of 3•+ . Theoretical calculations reveal the decisive role of vibronic coupling in shaping the potential energy surfaces on which the observed ring-opening reactions take place. Thus vibronic interaction in 1•+ mixes the 2 A 1 ′ ground state, characterized by its "non-bonding" 3a 1 ′ SOMO, with the 2 E′′ first excited state resulting in the destabilization of a lateral C-C bond and the initial formation of the methylenebicyclobutyl radical cation 5•+ . The further rearrangement of 5 •+ to 3 •+ occurs via 2 •+ and proceeds through two additional lateral C-C bond cleavages characterized by transition states of extremely low energy, thereby explaining the absence of identifiable intermediates along the reaction pathway. In these consecutive ring-opening rearrangements, the "non-bonding" bridgehead C-C bond in 1•+ is conserved and ultimately transformed into a normal bond characterized by a shorter C-C bond length. This work provides strong support for the Heilbronner-Wiberg interpretation of the vibrational structure in the photoelectron spectrum of 1 in terms of vibronic coupling.
Solid waste incineration accounts for a growing proportion of waste disposal in both developed and developing countries, therefore it is important to constrain emissions of greenhouse gases from these facilities. At five Swiss waste incineration facilities with grate firing, emission factors for N2O and CH4 were determined based on measurements of representative flue gas samples, which were collected in Tedlar bags over a one year period (September 2010-August 2011) and analysed with FTIR spectroscopy. All five plants burn a mixture of household and industrial waste, and two of the plants employ NOx removal through selective non-catalytic reduction (SNCR) while three plants use selective catalytic reduction (SCR) for NOx removal. N2O emissions from incineration plants with NOx removal through selective catalytic reduction were 4.3 ± 4.0g N2O tonne(-1) waste (wet) (hereafter abbreviated as t(-1)) (0.4 ± 0.4 g N2O GJ(-1)), ten times lower than from plants with selective non-catalytic reduction (51.5 ± 10.6g N2O t(-1); 4.5 ± 0.9g N2O GJ(-1)). These emission factors, which are much lower than the value of 120g N2O t(-1) (10.4g N2O GJ(-1)) used in the 2013 Swiss national greenhouse gas emission inventory, have been implemented in the most recent Swiss emission inventory. In addition, the isotopic composition of N2O emitted from the two plants with SNCR, which had considerable N2O emissions, was measured using quantum cascade laser spectroscopy. The isotopic site preference of N2O - the enrichment of (14)N(15)NO relative to (15)N(14)NO - was found to be 17.6 ± 0.8‰, with no significant difference between the two plants. Comparison to previous studies suggests SP of 17-19‰ may be characteristic for N2O produced from SNCR. Methane emissions were found to be insignificant, with a maximum emission factor of 2.5 ± 5.6g CH4 t(-1) (0.2 ± 0.5g CH4 GJ(-1)), which is expected due to high incinerator temperatures and efficient combustion.
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