G. Moreau et al., Theoretical study of the collision-induced fundamental absorption spectra of O-2-O-2 pairs for temperatures between 193 and 273 K, J QUAN SPEC, 64(1), 2000, pp. 87-107
Citations number
37
Categorie Soggetti
Spectroscopy /Instrumentation/Analytical Sciences
Journal title
JOURNAL OF QUANTITATIVE SPECTROSCOPY & RADIATIVE TRANSFER
A theoretical analysis of the collision-induced fundamental absorption spec
tra of O-2-O-2 pairs is presented for temperatures between 193 and 273 K. M
ost of the absorption arises from the long-range quadrupole and hexadecapol
e-induced dipole mechanisms for which accurate matrix elements are availabl
e from various other experimental measurements or from ab initio calculatio
ns. The line shape used is that obtained from quantum computations of the f
ar infrared collision-induced absorption of N-2, modified to include dips r
esulting from the effects of intercollisional interference. Several refinem
ents, including contributions from back-reaction and short-range induced-di
pole moments, can improve the agreement in certain spectral regions but do
not lead to significant improvement in the global fits to the experimental
data. The small structural features superimposed on the smooth continuum ca
n be modeled by the modified line shape but the half-widths of the dips hav
e a density dependence inconsistent with that arising from interference. On
the other hand, difference spectra obtained by subtracting the theoretical
results from the experimental data appear quite similar to those obtained
previously at low temperatures, leading to the conclusion that this structu
re is due to dimers. Further experimental results at higher temperatures an
d for O-2-N-2 pairs would be useful to validate this interpretation. (C) 19
99 Elsevier Science Ltd. All rights reserved.