6533b85efe1ef96bd12c05d8

RESEARCH PRODUCT

On the theoretical determination of the electron affinity of ozone

subject

description

Multiconfigurational electron correlation methods have been analyzed in order to theoretically compute the electron affinity (EA) of ozone. The near-degeneracy correlation effects, which are so important in O3 and O 3 − , have been described using complete active space (CAS) SCF wave functions. Remaining dynamic correlation effects are computed using second-order perturbation theory (the CASPT2 method). The best calculated adiabatic value (including zero-point energy corrections), 2.19 eV, is about 0.09 eV larger than the experimental value. Comparative studies using size-consistent coupled pair functional approaches (CPF and ACPF) have also been performed. The harmonic frequencies in O 3 − have been determined to be: ω1=992, ω2=572, and ω3=879 cm−1, which gives a zero-point energy of 0.151 eV.