THEORETICAL QUANTITATIVE SPECTROSCOPY: COMPUTER SIMULATION OF MOLECULAR SPECTRA

摘要

We present the results of theoretically simulating, by variational methods, rotation-vibration spectra of NH_3 and PH_3. The simulations carried out for NH_3 are based solely on ab initio calculations, i.e., they are purely theoretical and involve no fitting to experiment. The PH_3 simulations are made from a potential energy function refined to reproduce experimental data and from an ab initio dipole moment function. We show that our simulations reproduce observed rotation-vibration intensities with an accuracy approaching that obtained in fittings to these intensities in terms of models involving an effective dipole moment operator. Our results suggest that theoretical simulations of spectra are now close to attaining a level of accuracy where they can successfully compete with quantitative-spectroscopy measurements of intensities and thus assist in the interpretation of remote-sensing spectra.