Solvent effects on the absorption spectrum and recombination kinetics of diphenylcarbonyl oxide

The absorption spectra and rate constants of diphenylcarbonyl oxide recombi nation in a series of solvents and their binary mixtures were determined by flash photolysis. An increase in the solvent polarity causes hypsochromic shift of the maximum in the absorption spectrum of Ph2COO. The analysis of the solvent effect on the recombination rate constant in terms of the four- parameter Koppel-Palm equation shows that the reactivity of carbonyl oxide depends on both specific and non-specific solvations. Quantum chemical B3LY P/6-31G(d) calculations Of H2COO and PhHCOO carbonyl oxides as well as the complexes of H2COO with acetonitrile and ethylene in different media were p erformed using a polarized continuum model.