Nature of the Frontier Orbitals in Phosphine, Trimethylphosphine, and Trifluorophosphine

Shen Xiu Xiao*, William C. Trogler, D. E. Ellis, Ziva Berkovitch-Yellin

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

168 Scopus citations


The electronic structures of PH3, P(CH3)3, and PF3 have been examined with the aid of self-consistent multipolar Xα calculations (SCM-Xα-DV). There is excellent agreement between the theoretical and experimental ionization energies. When the transition-state procedure is used, first ionization potentials of 10.39, 8.41, and 12.19 eV are calculated for PH3, P(CH3)3, and PF3, respectively. Experimental values are 10.58, 8.58, and 12.27 eV, respectively. Plots of the highest and lowest unoccupied orbitals provide insight into the role of phosphorus donor ligands in transition-metal systems. Especially interesting is the Tr-symmetry p-d hybrid that comprises the lowest empty orbital in the 7r-acceptor PF3 ligand.

Original languageEnglish (US)
Pages (from-to)7033-7037
Number of pages5
JournalJournal of the American Chemical Society
Issue number24
StatePublished - Jan 1 1983

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry


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