ON THE DETERMINATION OF VIBRATIONAL AND ROTATIONAL CONSTANTS FROM HIGH RESOLUTION ELECTRONIC SPECTRA

Abstract

Although the theory of vibration-rotation effects in electronic spectra is well understood and the numerical tools necessary for the extraction of rotational and vibrational constants from the observed spectra are readily available, these tools have not yet been fully exploited. In this paper will be presented the results of numerical experiments, with both real and synthetic data, which have been designed to help answer several questions: how well are the Dunham constants determined from extensive $B_{v}$ data; how well can the experimental data be reproduced by limited models; and are the answers to these two questions compatible? It will also be shown that unless some care is taken, the results of calculations on $B_{v}$ values can be seriously misleading.