Ab Initio Calculation of Harmonic Force Fields and Vibrational Spectra for the 
Phosphine Oxides and Sulfides R3PY (R = H, F, CH3; Y = O, S)

Schneider, Winfried; Thiel, Walter; Komornicki, Andrew

doi:10.1021/j100331a016

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Ab Initio Calculation of Harmonic Force Fields and Vibrational Spectra for the Phosphine Oxides and Sulfides R₃PY (R = H, F, CH₃; Y = O, S)

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Schneider, W., Thiel, W., & Komornicki, A. (1988). Ab Initio Calculation of Harmonic Force Fields and Vibrational Spectra for the Phosphine Oxides and Sulfides R₃PY (R = H, F, CH₃; Y = O, S). The Journal of Physical Chemistry, 92(20), 5611-5619. doi:10.1021/j100331a016.

Cite as: https://hdl.handle.net/11858/00-001M-0000-0028-E2C3-F

Abstract

Ab initio self-consistent field calculations at the 6-31G* level are reported for the title compounds R₃PY and the corresponding phosphines R₃P. The calculated geometries, rotational constants, vibrational frequencies, centrifugal distortion constants, Coriolis coupling constants, and infrared band intensities are compared with the available experimental data. Detailed assignments are suggested for the vibrational spectra of the trimethyl compounds. The scaled theoretical interaction force constants for F₃P0 and F₃PS are believed to be more reliable than the current empirical ones. Predictions for H₃P0 are compared with recent results from a matrix-isolation study. Plots of the calculated infrared spectra at 300 K with rotational structure are presented for H₃P0 and H₃PS, as an aid to their spectroscopic identification in the gas phase. Trends in the calculated force constants and dissociation energies for PO and PS bonds are discussed.