Rotationally resolved pulsed field ionization photoelectron study of CO+(X 2Σ+,v+=0–42) in the energy range of 13.98–21.92 eV

We have obtained rotationally resolved pulsed field ionization–photoelectron (PFI-PE) spectra of CO in the energy range of 13.98–21.92 eV, covering the ionization transitions CO+(X 2Σ+,v+=0–42,N+)←CO(X 1Σ+,v″=0,N″). The PFI-PE bands for CO+ (X 2Σ+, v+=8–22, 24, and 28–39) obtained here represent the first rotationally resolved spectroscopic data for these states. The high-resolution features observed in the PFI-PE spectra allow the identification of vibrational bands for the CO+ (X 2Σ+, v+=10, 14, 15, 17, 18, 21, 24, 25, 29–31, 33, 35–37, and 39) states, which strongly overlap with prominent vibrational bands of the CO+(A 2Π3/2,1/2,B 2Σ+) states. The simulation using the Buckingham–Orr–Sichel model has provided accurate molecular constants for CO+(X 2Σ+,v+=0–42), including ionization energies, vibrational constants (ωe+=2218.8±3.5 cm−1, ωe+xe+=16.20±0.32 cm−1, ωe+ye+=0.074±0.011 cm−1, and ωe+ze+=−0.001 83±0.000 13 cm−1), and rotational constants [Be+=1.9797±0.0051 cm−1, αe+=0.0201±0.0011 cm−1, γe+=0.000 1...

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