Showing papers by "Bruce S. Ault published in 2002"

Matrix Isolation Study of the Reaction of CrCl2O2 with NH3: Synthesis and Characterization of ClCr(O)2NH2

Abstract: Initial and secondary intermediates in the reaction of CrCl2O2 with NH3 have been characterized by matrix isolation infrared spectroscopy and density functional calculations. Twin-jet co-deposition of these two reagents led to a series of infrared absorptions that are assigned to the 1:1 molecular complex between these two species. The shift of ν2 of NH3 in the complex was +218 cm-1, indicating that CrCl2O2 is a moderately strong Lewis acid. Irradiation of these matrices with light of λ > 300 nm led to complete destruction of the complex and the growth of a number of new bands. These are assigned to the ClCr(O)2NH2 species, as well as to HCl arising from destruction of the complex. Identification of these species was supported by isotopic labeling (15N and 2H), as well as by B3LYP/6-311G+(2d,3p) density functional calculations. Good agreement was observed between the experimental and computed frequencies.

Infrared matrix isolation and density functional theory study of intermediates in the reactions of OVCl3 and CrCl2O2 with H2O

Abstract: Initial and secondary intermediates in the reactions of OVCl3 and CrCl2O2 with H2O have been characterized by matrix isolation infrared spectroscopy and density functional calculations. Twin jet co-deposition of these reagents led to a series of infrared absorptions that are assigned to the 1:1 molecular complexes between these two species. Irradiation of these matrices with light of λ > 300 nm led to complete destruction of the bands of complexes, and the growth of a number of new bands. These are assigned to the Cl2V(O)OH and ClCr(O)2OH species, as well as to HCl arising from destruction of the complex. Identification of these species was supported by isotopic labeling (18O and 2H), as well as by B3LYP/6-311G+(d,2p) and B3LYP/LANL2DZ density functional calculations. Good agreement was observed between the experimental and computed frequencies. The overall yield of product was low for these system, and was probably a consequence of the low basicity of H2O.

Matrix Isolation and ab Initio Study of 1:1 Hydrogen-Bonded Complexes of H2O2 with HF, HCl, and HBr

Abstract: Matrix isolation infrared spectroscopy has been combined with MP2/aug‘-cc-pVDZ calculations to characterize the 1:1 hydrogen-bonded complexes between H2O2 and the hydrogen halides HF, HCl, and HBr....