Matrix isolation and ab initio study of 1 : 1 hydrogen-bonded complexes ofH2O2 with NH3 and N(CH3)(3)

Matrix isolation infrared spectroscopy has been combined with MP2/6-31+G(d, p) calculations to characterize the 1:1 hydrogen-bonded complexes between H 2O2 and the bases NH3 and N(CH3)(3). Most obvious from the spectra of these complexes and their deuterated analogues is the shift to lower frequency o f the hydrogen-bonded O-H or O-D stretching bands relative to the isolated monomers. The experimental shifts are in good agreement with the computed s hifts. Perturbation of the O-O-H bending mode was also observed, along with shifts of certain vibrational modes of the base subunits in the complexes. Surprisingly, the experimental intensities of the product bands are low wh en compared to other hydrogen-bonded systems and to the computed intensitie s.