Analysis of the broadening and shifting of diatomic molecules' spectral lines caused by the transitions into highly excited vibrational states

Halfwidths and lineshifts of hydrogen fluoride molecule for the case of self-broadening are investigated for the absorption lines caused by the transitions into highly excited vibrational states near the dissociation limit. It is found the wave functions of highly excited vibrational states are delocalized. Therefore, perturbation theory series become divergent and dipole moment and polarizability matrix elements cannot be calculated accurately. The halfwidths and lineshifts are estimated in the framework of full resonance approximation for HF-HF lines belonging to the highly lying vibrational bands. It is proved, that halfwidths decrease due to the variation of dipole moment function. The halfwidths decrease riches to 12% in the 0-22 band relatively to the 0-2 band. It is found, that lineshifts increase due to the mean polarizability rising is sometimes in highly lying bands relatively to the 0-2 band.© (2004) COPYRIGHT SPIE--The International Society for Optical Engineering. Downloading of the abstract is permitted for personal use only.