Ionization Potentials of the Tetraphosphorus Molecule

C. R. Brundle, K. A. Kuebler, M. B. Robin, Harold Basch

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81 Scopus citations


The He(I) and He(II) photoelectron spectra of the P4 molecule have been recorded and compared with the results of an ab initio calculation of the electronic structure using s- and p-type Gaussian orbital basis functions. The agreement for the first three ionization potentials is excellent and is taken to show that in a sufficiently good s,p basis, there is no need for 3d AO's, contrary to the claims of others. The “σ” bonds are unavoidably bent in a description which does not use (or need) 3d AO's. The first, second, and fourth ionizations show appreciable Jahn-Teller splitting, but vibrational structure is observed only in the third ionization (2A1, v1’ excited). The optical spectrum of P4 can be explained using configuration interaction among the valence-shell 1T2 configurations, and the low oscillator strengths of certain bands are shown to result from strong mixing among allowed transitions, rather than from symmetry restrictions. Electron density plots of the valence-shell MO's are also presented.

Original languageEnglish
Pages (from-to)20-25
Number of pages6
JournalInorganic Chemistry
Issue number1
StatePublished - 1 Jan 1972
Externally publishedYes


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