Photoionization processes at threshold. II. Threshold photoelectron, photoionization, and coincidence ion‐threshold photoelectron spectra of BF3

Threshold photoelectron spectra and photoionization efficiency curves have been measured for BF3 from the onset of ionization to 19.7 eV. This range includes four electronic states of BF+3. Vertical ionization energies of 15.96, 17.12, and 19.181 eV are observed for the first, third, and fourth states, respectively. The relative ionization cross sections for production of these states agree with those previously observed in the HeI photoelectron spectrum, but the cross section for ionization in the vicinity of the second state is considerably larger in the threshold photoelectron spectrum. The vibrational structure of the neutral BF3 molecule is not observed in either the first or third electronic states of BF3+, but the symmetric stretching mode progression appears in the band for the fourth state. It appears likely that production of each of the three lowest states of the ion involves a change in molecular geometry with respect to the ground state of the neutral. A breakdown curve was obtained between i...

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