Curve Crossing of theB3Σu− and 3Π u States of O2and Its Relation to Predissociation in the Schumann—Runge Bands

摘要: Nonempirical quantum mechanical calculations including electron correlation have been carried out for the lowest 3Σu− and 3Π u states of O2. A relatively large basis set is used 257 345 symmetry‐adapted configurations are included in first‐order wavefunctions. For B state, theoretical spectroscopic constants (with experimental values parentheses) Te 6.16 eV (6.17), De 0.76 (1.01), re 1.64A(1.60), ω e 679 cm−1 (709), Be 0.783 cm−1 (0.819). Neither state well described by a single configuration, seen to normal (non‐Rydberg) distribution. The calculated potential curves indicate that repulsive curve crosses inner limb curve. Analogous on 1Π yield crossing outer Since previous interpretations predissociation suggested limb, this discussed some detail....