Matrix isolation and ab initio study of the hydrogen-bonded complex between H2O2 and (CH3)(2)O

Matrix isolation infrared spectroscopy has been combined with MP2/6-31+G(d, p) calculations to characterize the 1:1 hydrogen-bonded complex between H2O 2 and (CH3)(2)O 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 com pare 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(CH 3)(2) complex are substantially larger than the perturbations reported prev iously for the analogous HOH:O(CH3)(2) complex, suggesting that H2O2 is a b etter 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(CH 3)(2).