화학공학소재연구정보센터
Journal of Physical Chemistry A, Vol.106, No.13, 3092-3101, 2002
Extraction of the vibrational dynamics from spectra of highly excited polyatomics: DCO
The effective spectroscopic Hamiltonian fitted to experiment by Troellsch and Temps (Z Phys. Chem. 2001, 215, 207) and describing high vibrational excitation to bound and resonant states is used in conjunction with methods of nonlinear classical dynamics and semiclassical mechanics to extract, for all of the observed highly excited resonance levels in polyad 8, the molecular motions upon which they are quantized, Two types of interlaced dynamically distinct ladders of states are revealed. The rungs of these ladders intersperse, making the spectra complex. The resonant 2:2:1 frequency ratio of the DC and CO stretches and the bend, respectively, is what causes the complexity and is what caused past attempts at interpretation to be at best incomplete, All states are assigned with physically meaningful quantum numbers corresponding to quasiconserved quantities. Most interestingly, it is pointed out that much of the information and assignment call be done without any calculations at all, using only the qualitative ideas from nonlinear, semiclassical, and quantum mechanics, along with the information supplied by the experimentalist.