Abstract
By employing the two-color visible–ultraviolet (vis–UV) laser pulsed field ionization–photoelectron (PFI–PE) measurement, we have obtained rotationally selected and resolved photoelectron spectra for the MoO+(X4Σ–; v+ = 0, 1, and 2) and MoO+(a2Δ3/2,5/2; v+ = 0 and 1) cationic states. The unambiguous rotational assignments have made possible the determination of highly precise values for the band origin v00+ = 60 147.9 ± 0.8 cm–1, rotation constant B0+ = 0.4546 ± 0.0006 cm–1, spin–spin coupling constant λ = 26.454 ± 0.017 cm–1, and bond length re+ = 1.642 ± 0.001 A for the MoO+(X4Σ–) ground state; v00+ = 60 556.4 ± 0.8 cm–1, B0+ = 0.4711 ± 0.0005 cm–1, and r0+ = 1.613 ± 0.001 A for the MoO+ (a2Δ3/2) excited state; and v00+ = 61 718.2 ± 0.8 cm–1, B0+ = 0.4695 ± 0.0006 cm–1, and r0+ = 1.616 ± 0.001 A for the MoO+ (a2Δ5/2) excited state. The ionization energy (IE) for MoO is determined to be IE(MoO) = 60 095.1 ± 0.8 cm–1 [7.4508 ± 0.0001 eV]. Furthermore, the vibrational constants are determined as ωe+ = 1000...
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