The CO2 complexes with HOO and HO in argon matrices Original Research Article

Complexes of the peroxy radical and the hydroxy radical with CO2 have been investigated with FTIR spectroscopy. The peroxy radical–CO2 complex was formed on the surface of growing argon matrices by codepositing peroxy radicals and CO2. The hydroxyl radical–CO2 complex was formed on photolysis (266 nm) of the matrix isolated peroxy radical–CO complex. The bands were identified from concentration dependencies, H to D shifts and by photolysis experiments. In the photolysis experiments the correlation coefficients between data series – decay and growth curves – and the degree of photolysis of the bands were calculated. Based on these data the bands were then assigned. The correlation coefficients also provided information about reactant/product relations. Ab initio calculations on the SCF level have been carried out in order to investigate the relations between complex structure and spectral shifts.