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Mass selected slow photoelectron spectra (SPES) of three boron-containing reactive species, BH 2 , BH, and BF were recorded by double imaging photoion-photoelectron coincidence spectroscopy (i 2 PEPICO) using synchrotron radiation. All species were generated in a flow reactor from the H-abstraction of B 2 H 6 by F atoms created in a F 2 microwave discharge. The spectrum of BH 2  + exhibits a long bending mode progression with a 970 cm -1 spacing due to the large geometry change from bent to linear upon ionization. Its ionization energy was determined as 8.12 ± 0.02 eV. For BH, photoionisation from both X 1 Σ + singlet and a 3 Π triplet state was observed, permitting the experimental determination of the singlet/triplet gap (ΔE ST ) from the observed IE's of 9.82 eV and 8.48 eV. In addition, a threshold photoelectron spectrum of BF was recorded, which leads to an IE of 11.11 eV and an improved value for ν BF  + of 1690 cm -1 . All spectra were simulated by calculating Franck-Condon factors from optimised structures based on quantum chemical calculations.

Photoelectron spectroscopy of boron-containing reactive intermediates using synchrotron radiation: BH2, BH, and BF

Photoelectron spectroscopy of boron-containing reactive intermediates using synchrotron radiation: BH₂, BH, and BF