Computer Science
Scientific paper
Jun 1998
adsabs.harvard.edu/cgi-bin/nph-data_query?bibcode=1998aipc..430..110m&link_type=abstract
The eleventh international conference on fourier transform spectroscopy. AIP Conference Proceedings, Volume 430, pp. 110-127 (1
Computer Science
Organic Compounds, Polymers, Decomposition Reactions
Scientific paper
Fourier transform infrared spectroscopy at unapodized resolutions up to 0.0018 cm-1 has been used to probe the ro-vibrational energies, chemistry and structures of short lived molecular species. A number of methods for generation of transients, typically flow pyrolysis, photolysis and IR laser powered pyrolysis (IRLPP) have been coupled with a Bruker HR120 FTIR system and vibration-rotation spectra of molecules with lifetimes ranging from NCN(t1/2~10-3 sec) through C3O(t1/2<1 sec), propadienone (t1/2~10 sec) and vinylamine (t1/2~10 min) to difluoroacetylene (t1/2~30 min.) and chlorophosphaethyne (t1/2~30 min.) have been recorded. For asymmetric molecules in particular, assignment of a spectral band is often complicated because just a single band can contain thousands of resolved vibration-rotation lines. Computer assisted assignment of the spectra of species ranging from simple linear molecules, through near symmetric tops to highly asymmetric tops is discussed. In addition to using computer aided assignment to deal with the plethora of lines an experimental alternative has been used to reduce the number of lines. We have built a system based on a supersonic jet expansion coupled to our Bruker HR120 spectrometer and have used this to cool species down to 1/2 a rotational temperature of typically 20-60 K. The prospects of using this system to study the spectra of transient molecules are discussed.
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