Direct fit of experimental ro-vibrational intensities to the dipole moment function: Application to HCl

A dipole moment function (DMF) for hydrogen chloride (HCl) has been obtained using a direct fit approach that fits the best available and appropriately weighted experimental data for individual ro-vibrational transitions. Combining wavefunctions derived from the Rydberg–Klein–Rees (RKR) numerical method and a semi-empirical DMF, line intensities were calculated numerically for bands with Δ v=0, 1, 2, 3, 4, 5, 6, 7 up to v′=7. The results have demonstrated the effectiveness of inclusion of rotational dipole moment matrix elements and appropriate weighting of the experimental data in the DMF fitting. The new method is shown to be superior to the common method of fitting only the rotationless dipole moment elements, while at the same time being simple to implement. ► New method to fit data for individual transitions to the dipole moment function. ► Verification of the effectiveness of the new method in application to H 35Cl. ► Severe errors in some of the previous publications unveiled.