PH 3 revisited: Theoretical transition moments for the vibrational transitions below [formula omitted

Abstract

We present here an extensive list of theoretical vibrational transition moments for the electronic ground state of PH 3, covering all transitions with significant intensities in the wavenumber region below 7000 cm - 1 . This work complements, and uses a potential energy surface from, our recent calculation of vibrational term values for PH 3 [R.I. Ovsyannikov, W. Thiel, S.N. Yurchenko, M. Carvajal, P. Jensen, J. Chem. Phys. 129 (2008) 044309] and it extends, and uses a dipole moment surface from, our previous work on PH 3 intensities [S.N. Yurchenko, M. Carvajal, W. Thiel, P. Jensen, J. Mol. Spectrosc. 239 (2006) 71–87]. Owing to an improved potential energy surface, the transition-moment results of the present work constitute a significant improvement over our previous work. The quality of the reproduction of the available experimental data suggests that we are approaching a situation where theoretical calculations of intensity information can compete with, and possibly in some cases replace, experimental determinations of intensities for small molecules. We demonstrate that the theoretical intensity results of the present work are in accordance with the predictions of local-mode theory.