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Keywords:

Science & Technology, Physical Sciences, Chemistry, Physical, Physics, Atomic, Molecular & Chemical, Chemistry, Physics, 02 Physical Sciences, 03 Chemical Sciences, 09 Engineering, Chemical Physics, 34 Chemical sciences, 40 Engineering, 51 Physical sciences

Abstract:

A theoretical characterization has been performed for the molecular structures, vibrational and hyperfine constants and electronic properties of the simplest model phosphinoyl (H2P=O)• and thiophosphinoyl (H2P=S)• radicals in their ground (2A′) and electronically excited (2A″) states. Ab initio calculations have been carried out at the Hartree-Fock, Møller-Plesset (MP) perturbation theory and configuration interaction (CI) levels employing basis sets of various sizes. Available experimental data derived mostly from IR, UV and ESR spectroscopies of substituted radicals are compared and commented on. In particular, the origin of the UV absorption bands centered around 330-340 nm and values for the 17O isotope hyperfine splitting constants and the P-O stretching frequencies in phosphinoyl radicals are discussed in detail. The rearrangements leading to the dicoordinated P compounds (HPOH and HPSH) have also been considered. The latter are shown to be more stable than their respective tricoordinated isomers. © 1989.