RESUMO
The 193-nm photolysis of CH2CHCN illustrates the capability of chirped-pulse Fourier transform millimeter-wave spectroscopy to characterize transition states. We investigate the HCN, HNC photofragments in highly excited vibrational states using both frequency and intensity information. Measured relative intensities of J = 1-0 rotational transition lines yield vibrational-level population distributions (VPD). These VPDs encode the properties of the parent molecule transition state at which the fragment molecule was born. A Poisson distribution formalism, based on the generalized Franck-Condon principle, is proposed as a framework for extracting information about the transition-state structure from the observed VPD. We employ the isotopologue CH2CDCN to disentangle the unimolecular 3-center DCN elimination mechanism from other pathways to HCN. Our experimental results reveal a previously unknown transition state that we tentatively associate with the HCN eliminated via a secondary, bimolecular reaction.
RESUMO
A Chirped-Pulse millimeter-Wave (CPmmW) spectrometer is applied to the study of chemical reaction products that result from pyrolysis in a Chen nozzle heated to 1000-1800 K. Millimeter-wave rotational spectroscopy unambiguously determines, for each polar reaction product, the species, the conformers, relative concentrations, conversion percentage from precursor to each product, and, in some cases, vibrational state population distributions. A chirped-pulse spectrometer can, within the frequency range of a single chirp, sample spectral regions of up to â¼10 GHz and simultaneously detect many reaction products. Here we introduce a modification to the CPmmW technique in which multiple chirps of different spectral content are applied to a molecular beam pulse that contains the pyrolysis reaction products. This technique allows for controlled allocation of its sensitivity to specific molecular transitions and effectively doubles the bandwidth of the spectrometer. As an example, the pyrolysis reaction of ethyl nitrite, CH3CH2ONO, is studied, and CH3CHO, H2CO, and HNO products are simultaneously observed and quantified, exploiting the multi-chirp CPmmW technique. Rotational and vibrational temperatures of some product molecules are determined. Subsequent to supersonic expansion from the heated nozzle, acetaldehyde molecules display a rotational temperature of 4 ± 1 K. Vibrational temperatures are found to be controlled by the collisional cooling in the expansion, and to be both species- and vibrational mode-dependent. Rotational transitions of vibrationally excited formaldehyde in levels ν4, 2ν4, 3ν4, ν2, ν3, and ν6 are observed and effective vibrational temperatures for modes 2, 3, 4, and 6 are determined and discussed.
