Isotopic and symmetry breaking effects on phosphine spectra under H → D substitutions from ab initio variational
Dominika Viglaska1, Michael Rey1, Andrei V Nikitin2
1Groupe de Spectrométrie Moléculaire et Atmosphérique, UMR CNRS 7331, BP 1039, F-51687 Reims Cedex 2, France.
Abstract:
Variationally computed infrared spectra in the range [0-5000] cm-1 are reported for the deuterated PH2D and PHD2 molecules from accurate potential energy and dipole moment surfaces initially derived for the major isotopologue PH3( ). Energy level and line intensity calculations were performed by using a normal-mode model combined with isotopic and symmetry transformations for the H → D substitutions. Theoretical spectra were computed at 296 K up to J max = 30 and will be made available through the TheoReTS information system (http://theorets.univ-reims.fr, http://theorets.tsu.ru). For the very first time, ab initio intensity predictions of PH2D/PHD2 are in good qualitative agreement with the literature. This work will be useful for spectral intensity analysis for which accurate spectral intensity data are still missing.
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