A high-level ab initio study has been performed on the conformational structure and vibrational spectra of HO2NO2. Calculations carried out with coupled-cluster methods using a series of Pople and Dunning basis sets reveal that there is a significant basis set dependence on the predicted ab initio structure. Higher angular momentum basis sets are shown to be necessary in order to bring the calculated structure into agreement with experimental rotational constants. Harmonic vibrational frequencies of HO2NO2 are computed at the CCSD(T)/aug-cc-pVTZ level of theory while the corresponding vibrational anharmonicities are calculated at the MP2/cc-pVTZ level. In addition, the absorption cross sections of OH stretching overtones in HO2NO2 are calculated using a dipole function computed at the QCISD level of theory and found to be in good agreement with the available experimental data. (C) 2004 American Institute of Physics.