Matrix Isolation and ab Initio Study of the Hydrogen-Bonded Complex between H2O2 and (CH3)2O

Matrix isolation infrared spectroscopy has been combined with MP2/6-31+G(d,p) calculations to characterize the 1:1 hydrogen-bonded complex between H2O2 and (CH3)2O. The O−H stretching mode was observed to red shift 234 cm-1 upon hydrogen bond formation, while a 45 cm-1 blue shift was noted for the O−O−H bending mode of the H2O2 subunit in the complex. These values compare well to the computed shifts of −293 and +20 cm-1, respectively. The perturbations to the vibrational modes of the two subunits in the HOOH:O(CH3)2 complex are substantially larger than the perturbations reported previously for the analogous HOH:O(CH3)2 complex, suggesting that H2O2 is a better proton donor for hydrogen bonding than H2O. In contrast, band shifts in HOOH:O(CH3)2 are much less than observed for FH:O(CH3)2 and ClH:O(CH3)2.