Multireference configuration interaction studies on higher valence and Rydberg states of OClO, ionization potentials, and electron detachment energies

摘要

MRCI results are reported for the vertical excitation energies (VEE) and oscillator strengths f of doublet states of OClO up to 11 eV, including 3b1 → 4s, 4p, 3d, 5s, 5p, 4d, and most 1a2, 8a1, 5b2 → 4s and 4p Rydberg states. The lowest Rydberg states 3b1 → 4s and 3b1 → 4px have mixed valence-Rydberg character. The observed spectral bands were reassigned to include valence states which have generally higher oscillator strengths. The well-known valence state 12A2 has a VEE of 3.63 eV, and a relatively high f of 0.042. Overall, the calculated oscillator strengths are in good agreement with measured values. The lowest quartet state, 14B2, lies at 6.95 eV. Quartet Rydberg states start with 1a2 → 4s at 9.28 eV. According to calculated vertical ionization potentials (VIP) of OClO, the second VIP at 12.59 eV is reassigned from 13B1 to 13B2 (ionization from 1a2, rather than 8a1), and the third VIP at 12.63 eV from 11B1 to 13B1 (ionization from 8a1). Vertical electron detachment energies of OClO− have been calculated up to 8.9 eV. There is good agreement with experimental values.