ISSN:
1089-7690
Source:
AIP Digital Archive
Topics:
Physics
,
Chemistry and Pharmacology
Notes:
The ion yield curves of PH+3, PH+2, and PH+ from photoionization of PH3 have been measured. The free radical PH2 has been generated by pyrolysis, and the ion yield curve of PH+2 (PH2) determined. These measurements yield directly I.P. (PH3)=9.870±0.002 eV, and I.P. (PH2)=9.824±0.002 eV. In addition, we deduce D0 (H2P–H)=82.46±0.46 kcal/mol, D0 (HP–H)=74.2±2 kcal/mol, D0 (P–H)=70.5±2 kcal/mol, I.P. (PH)=10.18±0.1 eV, and other thermochemically related quantities. The ionization energies of PH, PH2, and PH3 are computed by ab initio molecular orbital methods to fourth order in Møller–Plesset theory, and are found to be in good agreement with experiment. The ground state of PH+2 is inferred to be 1A1, with the 3B1 state higher by ≥0.71 eV. This ordering is the reverse of that in CH2 and NH+2.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1063/1.450147
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