Abstract
Resonance enhanced two photon ionization study in a pulsed molecular beam identified spin-forbidden transitions of the 2 3Πu(1u)–X 1Σg+(0g+) and 2 3Πu(0u+)–X 1Σg+(0g+) of Rb2. Λ-doubling and interference-induced rotational branch intensity anomalies are observed for 2 3Πu(1u)–X 1Σg+(0g+) transitions. The rotational constant for the 2 3Πu state was determined to be Be=0.018 932 5±0.000 007 4 cm−1 for Rb285, giving Re=4.5796±0.0009 Å. Other molecular parameters for Rb285 are determined as Te=19 784.254±0.009 cm−1, ωe=42.200±0.006 cm−1, ωexe=0.171±0.001 cm−1, and ωeye=−0.001 06±0.000 06 cm−1 for the 2 3Πu(0u+) state and Te=19 785.74±0.01 cm−1, ωe=42.297±0.005 cm−1, ωexe=0.1725±0.0009 cm−1, and ωeye=−0.000 78±0.000 04 cm−1 for 2 3Πu(1u) state. These Re, ωe, and Te values agree well with ab initio calculated values. The spin–orbit coupling constant A and Λ-doubling parameters p and q are determined by simultaneous fitting of the rotational structures of both 2 3Πu(1u)−X 1Σg+ and 2 3Πu(0u+)−X 1Σg+ transitions.
Published Version
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