Vacuum synthesis and determination of the ionization energies of different molecular orbitals for BrOBr and HOBr

Abstract

Rovibrationally selected and resolved pulsed field ionization-photoelectron study of propyne: Ionization energy and spin-orbit interaction in propyne cation J. Chem. Phys. 128, 094311 (2008) Pure BrOBr and HOBr were synthesized in vacuum by heterogeneous reactions of the dried bromine vapor and Br 2 /H 2 O mixture vapors ͑5:1͒ with HgO, respectively, and then characterized by He I photoelectron spectroscopy ͑PES͒ and augmented by ab initio GAUSSIAN 2 and the outer valence Green's functional calculations. The first PE band at 10.26 eV with vibrational spacing 550Ϯ60 cm Ϫ1 and the second PE band at 11.23 eV with vibrational spacing 240Ϯ60 cm Ϫ1 are, respectively, assigned as ionizations of the electrons of the highest occupied molecular orbital ͑HOMO͒ (6b 1 (39)) and the SHOMO(13b 2 (38)) orbitals of BrOBr. The first PE band at 10.73 eV with vibrational spacing 750Ϯ60 cm Ϫ1 and the second PE band at 11.56 eV with vibrational spacing 650Ϯ60 cm Ϫ1 are, respectively, assigned as ionizations of the electrons of the HOMO(6aЉ (22)) and the SHOMO(16aЈ(21)) orbitals of HOBr. The study does not only provide vacuum synthesis conditions for preparing pure BrOBr and HOBr, but also provide experimental PES results along with theoretical ionization energies of different molecular orbitals for BrOBr and HOBr.

Disproportionation of Bromous Acid HOBrO by Direct O-Transfer and via Anhydrides O(BrO)2and BrO–BrO2. An Ab Initio Study of the Mechanism of a Key Step of the Belousov–Zhabotinsky Oscillating Reaction

“…The potential energy surfaces of HBrO, , HBrO 2 , , and HBrO 3 , have been explored previously, mostly with a view to atmospheric chemistry. The isomers HOBr, HOBrO, and HOBrO 2 are pertinent in the current context and molecular models are shown in Figure .…”

Novel gaseous transient species: Generation and characterization

“…(8) and (9). However, as for the laboratory studies on its physical chemistry properties, it can be prepared through the hydrolysis of BrOBr [28] . Although many molecular structural properties of HOBr have been reported, the electronic structure in the gas phase remains unknown, due to its instability in the gas phase with high purity.…”

“…We approached this problem through the vacuum heterogeneous reaction of Br 2 /H 2 O mixture (5︰1) with activated HgO [28] . Experimental details are as follows: the evacuated flask with freshly prepared and thermally activated HgO was successively filled with bromine vapor (150 Torr) and H 2 O (30 Torr) at 30℃ in the dark.…”

Theoretical Study on the Coupling Mode of BrOH2O and HOBrH2O Complexes

“…1 The studies of bromine-containing species [2][3][4][5][6][7][8][9] are less than those of the chlorine-containing species, 3,4,10-12 although Wennberg's 13 studies have shown that catalysis involving bromine-containing species accounts for as much as 30% of the total halogen-controlled loss of the strospheric ozone in Antarctic Circle. In terms of ozone destruction, moreover, bromine-containing species is 100 times more efficient than chlorine-containing species on a mole-per-mole basis.…”