Title

Neon matrix ESR and CI theoretical investigation of 10BF+ and 11BF+: Photoionization of BF from reactive laser sputtering and high temperature sources

ACS Citation

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.

Abstract

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.

Source Name

Journal of Chemical Physics

Publication Date

1-1-1986

Volume

85

Issue

10

Page(s)

3521-3525

Document Type

Citation

Citation Type

Article