Abstract
A theoretical characterization has been performed for the molecular structure, rotational and vibrational constants of the simplest thioxophosphane HPS and its isomer thiohydroxyphosphinidene HSP in their lowest-lying singlet, triplet and ionized (HPS †, HSP † states. Geometries were optimized at both the HF and MP2/6–31G(d, p) leves, whereas harmonic vibrational frequencies were computed at HF/–31(d). Empirical corrections were made, when possible, on these calculated values in order to provide a more realistic prediction. HPS has a singlet ground state with a triplet-singlet separation of 24.4 kcal mol −1 and a first ionization energy (IE a) of 9.14 eV. HSP has a triplet ground state ( 3A″) with a rather small singlet-triplet gap (10.7 kcal mol −1) and a smaller IE a (8.14 eV). The radical cations present a reversed stability ordering as compared to their neutral counterparts. This results from a difference in proton affinities and binding energies of relevant species. Relative energies between stationary estimated at the MP4 SDQ/6–31+ +G(2d,p) level suggest that all equilibrium structures considered are relatively stable with respect to unimolecular rearrangement making them detectable in inert matrix at low temperature.
Published Version
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