Neon matrix ESR and CI theoretical investigation of 10BF+ and 11BF+: Photoionization of BF from reactive laser sputtering and high temperature sources
Knight, L. B.; Ligon, A. R.; Cobranchi, S. T.; Cobranchi, D. P.; Earl, E. A.; Feller, D.; Davidson, E. R. Neon matrix ESR and CI theoretical investigation of 10BF+ and 11BF+: Photoionization of BF from reactive laser sputtering and high temperature sources. J. Chem. Phys. 1986, 85, 5437-5437.
The 1 1BF+ and 1 0BF+ radical cations have been generated and trapped in neon matrices at 4 K using the combined techniques of pulsed reactive laser sputtering and photoionization at 16.8 eV. An independent high temperature source of BF(g) in conjunction with photoionization was also employed and a comparison between these two different generation methods reveals no significant differences in their ESR spectra. The magnetic parameters for 1 1BF+ measured in neon matrices are g -ˆ¥=2.0012(3), g -Š¥=2.0004(3), (1 1B) A -ˆ¥=1784(1), and A -Š¥=1727(1) MHz, (1 9F)A -ˆ¥=410(1), and A -Š¥=152(1) MHz. Extensive a b i n i t i otheoretical calculations have been conducted for BF+ and the nuclear hyperfineproperties obtained from various types of CI wave functions show excellent agreement with the experimental measurements. Valence orbital occupancies obtained from a Mulliken-€type population analysis performed on the CI wave functions are compared with the conventional free atom comparison method for obtaining electronic structure information from ESRAtensor measurements. The distribution of the unpaired electron in BF+ is compared to six other isoelectronic first row radicals.
Journal of Chemical Physics