A HIGH RESOLUTION SPECTROSCOPIC STUDY OF ABSORPTION LINE PROFILES IN THE A-BAND OF MOLECULAR OXYGEN (LASER).

摘要

A study has been made of absorption line profiles in the A-band of molecular oxygen at 13120 cm('-1). High resolution spectra were obtained using a narrow linewidth tunable dye laser in conjunction with a multi-pass optical absorption cell, a photo-acoustic cell, and a variable temperature photo-acoustic cell. Line parameters were determined using a least-squares fitting routine which numerically adjusted parameters of certain standard line profile functions to obtain the best fit with the observed profiles. The standard line profiles used were the Voigt function, two Dicke-narrowed profiles, and a speed dependent Voigt profile. Clear deviations are shown between the observed and simple Voigt profiles, while the other three profiles were found to fit the observed profiles well. Line strengths, pressure broadening coefficients, and pressure induced frequency shifts were also determined from the measured profiles. Line strengths obtained from the absorption measurements are compared with expressions given by Childs and Mecke (1931), Schlapp (1932;1937), Tilford et al. (1965) and Watson (1968). The expressions of Tilford et al. (1965) and Watson (1968) are shown to be in closest agreement with the measurements. Self-broadening coefficients are compared with previous measurements made by other investigators as well as with theoretical calculations made using the semi-classical method of Smith and Giraud (1979). Pressure induced frequency shifts were determined by taking simultaneous spectra of two cells at different pressures. The pressure induced frequency shifts and broadening coefficients were measured in pure oxygen as a function of temperature (-20(DEGREES)C to 100(DEGREES)C), as well as in air and the broadeners He, Ne, Ar, Kr, and Xe at ambient temperature. The measured gas broadening coefficients are shown to be in close agreement with values calculated using the method of Smith and Giraud (1979). It is also shown that the general behavior observed for the pressure induced frequency shifts can be obtained by allowing the absorber-perturber interaction potential to change between the ('3)(SIGMA) ground state and the ('1)(SIGMA) excited state of the O(,2) molecule.