Force-field calculation and geometry of the HOOO radical

High-level ab initio calculations using the Davidson-corrected multireference configuration interaction (MRCI) level of theory with Dunning's correlation consistent basis sets and force-field calculations were performed for the HOOO radical. The harmonic vibrational frequencies and their anharmonic constants obtained by the force-field calculations reproduce the IR-UV experimental vibrational frequencies with errors less than 19 cm(-1). The rotational constants for the ground vibrational state obtained using the vibration-rotation interaction constants of the force-field calculations also reproduce the experimentally determined rotational constants with errors less than 0.9%, indicating that the present quantum chemical calculations and the derived spectroscopic constants have high accuracy. The equilibrium structure was determined from the experimentally determined rotational constants combined with the theoretically derived vibration-rotation interaction constants. The determined geometrical parameters agree well with the results of the present MRCI calculation. (C) 2013 AIP Publishing LLC.