The reaction of SF6 with thermal electrons has been studied in a Ni-63 atmospheric pressure ionization source for a quadrupole mass spectrometer (API/MS). The major ions that are observed are the parent negative ion (SF−6) and the parent minus a fluorine atom (SF−5). The ratio of [SF−5]/[SF−6] is highly temperature dependent above 500 K. The dissociation energy of the ground state negative ion into SF−5 and F has been determined to be 1.35±0.1 eV. This gives values of 3.8±0.15 eV for the electron affinity of SF5 and 1.15±0.15 eV for the electron affinity of SF6. The negative ion states of sulfur hexafluoride have been described by ‘‘pseudo-two-dimensional’’ Morse potentials calculated using experimental data.
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