Abstract

Three-dimensional potential energy and dipole moment surfaces have been calculated for the 25 electron radicals NF2 and O−3 in their 2B1 ground electronic states by the complete active space self-consistent field (CASSCF) method with basis sets of 87 (NF2) and 99 (O−3) contracted Gaussian-type orbitals. Spectroscopic constants have been calculated from the analytical potential energy functions for each species, and the results for NF2 are compared to the available experimental data. Predictions of the rotational and rotational–vibrational spectra of O−3 have been made by comparison to the NF2 results. Vibrational band origins have been calculated by perturbation theory and also variationally in a basis of distributed Gaussian functions. Rotationless dipole moment matrix elements and vibrational band intensities have been determined from the CASSCF dipole moment functions. The fundamental vibrational band origins and intensities of O−3 are predicted to be 979 cm−1/0.87 cm−2 atm−1 (ν1), 565 cm−1/17.8 cm−2 atm−1 (ν2), and 739 cm−1/2620 cm−2 atm−1 (ν3). Smaller basis set calculations of the first three excited electronic states of O−3 have also been carried out, and the results are compared to previous photodissociation experiments.

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