Analysis of experimental spectra of phosphine in the Tetradecad range near 2.3 μm using ab initio calculations

A V Nikitin; A Campargue; A E Protasevich; M Rey; K Sung; Vl G Tyuterev

doi:10.1016/j.saa.2023.122896

Analysis of experimental spectra of phosphine in the Tetradecad range near 2.3 μm using ab initio calculations

Spectrochim Acta A Mol Biomol Spectrosc. 2023 Dec 5:302:122896. doi: 10.1016/j.saa.2023.122896. Epub 2023 May 25.

Authors

A V Nikitin¹, A Campargue², A E Protasevich³, M Rey⁴, K Sung⁵, Vl G Tyuterev³

Affiliations

¹ Laboratory of Theoretical Spectroscopy, V.E. Zuev Institute of Atmospheric Optics, SB RAS, 1, Academician Zuev square, 634021 Tomsk, Russia. Electronic address: avn@iao.ru.
² Univ. Grenoble Alpes, CNRS, LIPhy, 38000 Grenoble, France.
³ Laboratory of Theoretical Spectroscopy, V.E. Zuev Institute of Atmospheric Optics, SB RAS, 1, Academician Zuev square, 634021 Tomsk, Russia.
⁴ Groupe de Spectrométrie Moléculaire et Atmosphérique, UMR CNRS 7331, Université de Reims, U.F.R. Sciences, B.P. 1039, 51687 Reims Cedex 2, France.
⁵ Jet Propulsion Laboratory, California Institute of Technology, 4800 Oak Grove Drive, Pasadena, CA 91109, USA.

PMID: 37331254
DOI: 10.1016/j.saa.2023.122896

Abstract

Due to its major interest for the chemistry of planetary atmospheres and exobiology, accurate spectroscopy data of phosphine are required for the search of signatures of this molecule in astronomical observations. In this work, high resolution infrared laboratory spectra of phosphine were analyzed for the first time in the full Tetradecad region (3769-4763 cm^-1) involving 26 rotationally resolved bands. Overall, 3242 lines were assigned in spectra previously recorded by Fourier transform spectroscopy at temperatures 200 K and 296 K, using a combined theoretical model based on ab initio calculations. The total nuclear motion Hamiltonian of PH₃ including ab initio potential energy surface, was reduced to an effective Hamiltonian using the high-order contact transformation method adapted to vibrational polyads of the AB₃ symmetric top molecules, followed by empirical optimization of the parameters. At this step, the experimental line positions were reproduced with a standard deviation of 0.0026 cm^-1 that provided unambiguous identification of observed transitions. The effective dipole transition moments of the bands were obtained by fitting to the intensities obtained from variational calculations using the ab initio dipole moment surface. The assigned lines were used to newly determine 1609 experimental vibration-rotational levels up to J_max = 18 with energy in the range 3896-6037 cm^-1 that represents significant extension towards higher energies compared to previous works. Transitions for all 26 sublevels of the Tetradecad were identified but with noticeably fewer transitions for fourfold excited bands because of their weaker intensity. At the final step, pressure-broadened half widths were attached to each transition and a composite line list adopting ab initio intensities and empirical line positions corrected to the accuracy of about 0.001 cm^-1 for strong and medium transitions was validated against experimental spectra available in the literature.

Keywords: Ab initio dipole; Contact Transformations method; Effective Hamiltonian; High energy levels; Infrared spectra; Jovian planets; Line intensities; Phosphine; Resonance interactions.