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 H(2)O(2) and (CH(3))(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 H(2)O(2) 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(CH(3))(2) complex are substantially larger than the perturbations reported previously for the analogous HOH:O(CH(3))(2) complex, suggesting that H(2)O(2) is a better proton donor for hydrogen bonding than H(2)O. In contrast, band shifts in HOOH:O(CH(3))(2) are much less than observed for FH:O(CH(3))(2) and ClH:O(CH(3))(2).