Journal of Chemical Physics, Vol.115, No.5, 2101-2108, 2001
Rotational-resolved pulsed field ionization-photoelectron study of NO+(A ' (1)Sigma(-),v(+)=0-17) in the energy range of 17.70-20.10 eV
We have obtained partially rotationally resolved pulsed field ionization-photoelectron (PFI-PE) spectra of NO in the energy range of 17.70-20.10 eV, covering ionization transitions of NO+(A' (1)Sigma (-),v(+)=0-17,J(+))<-- NO(X (2)Pi (3/2,1/2),v'=0,J'). The PFI-PE bands for NO+(A' (1)Sigma (-),v(+)=0-17) obtained here represent the first spectroscopic data that allow the direct determination of rotational constants for these states. As in previous studies, the PFI-PE bands are simulated using the Buckingham-Orr-Sichel model as an empirical scheme to derive reliable spectroscopic constants. The simulation, together with comparison with previous He I photoelectron data, has also provided information on intensity enhancements of PFI-PE bands. Accurate spectroscopic constants for NO+(A' (1)Sigma (-),v(+)=0-17) obtained in the present study include ionization energies, vibrational constants (omega (e)=1272.03 +/-1.45 cm(-1), omega (e)chi (e)=11.924 +/-0.188 cm(-1), and omega (e)y(e)=-0.059 +/-0.007 cm(-1)), and rotational constants [B-e=1.3562 +/-0.0024 cm(-1), alpha (e)=0.017 80 +/-0.000 61 cm(-1), and gamma (e)=-(1.574 +/-0.328)x10(-4) cm(-1)]. The simulation indicates that continuum photoelectron states can be formed with orbital angular momenta l up to 5, which corresponds to the maximum total angular momentum transfer of \DeltaJ\=13/2. Since the dominant rotational branches observed are DeltaJ=+/-1/2, +/-3/2, +/-5/2, +/-7/2, and +9/2, we conclude that continuum photoelectron states are predominantly produced in l=0-3 in the threshold photoionization of NO(X (2)Pi (3/2,1/2)) to form NO+(A' (1)Sigma (-),v(+)=0-17).