화학공학소재연구정보센터
Journal of Chemical Physics, Vol.119, No.6, 3219-3233, 2003
High resolution absorption spectrum of jet-cooled OCS between 64000 and 91000 cm-1
The absorption spectrum of jet-cooled OCS was photographed from 190 to 110 nm at a resolution limit of 0.0008 nm. No band maximum was observed between 190 and 156 nm, i.e., below 64 000 cm(-1). Ab initio calculations of the electronic energies and transition moments were carried out, including spin-orbit interaction, in the frozen core approximation. Rydberg states considered have ionic core X (2)Pi and principal effective quantum number n(*)=2-5.5, electronic angular momentum l=0-5. Up to n(*)=3.5, l=0-2, calculations were also done in the coupled electron pair approximation. It is shown that in OCS, like in N2O, CO2 or CS2, nppi (1)Sigma(+) states are at lower energy than npsigma(1,3)Pi. From the doublet structure shown by the corresponding transition origin bands, the rotational constant of the 4psigma(1,3)Pi and 4ppi (3)Sigma(-) states was deduced to be B-0(')=0.1940(5) cm(-1). Transitions involving excitation to ns or nd Rydberg orbitals, allowed in the less-symmetric molecules, were calculated to have relative intensities respectively two and three orders of magnitude greater in OCS than in N2O. The ns series could be assigned only to medium intensity or weak bands. In contrast, nddelta(1)Pi transitions were assigned to relatively strong bands and could be followed up to n about 20. Previous low-resolution absorption and electron-impact spectra are reviewed. Most of the present assignments agree with those of resonance enhanced multiphoton ionization spectra and satisfactory assignments are obtained for the 15 unassigned electronic origins observed by Morgan [J. Chem. Phys. 105, 2141 (1996)]. (C) 2003 American Institute of Physics.