On determination of electronic-vibro-rotational term values of diatomic molecules from measured wavenumbers

Abstract

A method is proposed for determining rovibronic term values of diatomics from experimental data on the wavenumbers of electronic-vibro-rotational spectral lines. In contrast to existing techniques, the new one is based on the Rydberg-Ritz principle only. It is shown that a link between a set of rovibronic term values and a set of wavenumbers of observed rovibronic spectral lines appears when three and more different electronic-vibrational states are pairwise-connected by radiative transitions. The method differs from known techniques in several aspects, namely, it: 1) doesn't need any assumptions concerning an internal structure of a molecule; 2) doesn't involve any intermediate parameters (as molecular constants in traditional techniques); 3) gives an opportunity to use in one-stage optimization procedure all available experimental data obtained for various band systems, by various authors, and in various works; 4) provides in an interactive mode the opportunity to select the experimental values, eliminating rough errors, to revise wrong identifications of spectral lines and to compare various sets of experimental data for mutual consistency; 5) allows to obtain not only an optimal set of rovibronic term values, but also the error bars depending on quantity and quality of existing experimental data. Necessary precondition for use of this method is a preliminary identification of electronic-vibro-rotational lines to certain electronic-vibro-rotational radiative transitions. For this purpose one has to use traditional methods of the analysis of molecular spectra.