1. Rotationally resolved vacuum ultraviolet pulsed field ionization-photoelectron vibrational bands for HD+(X 2Σg+,v+=0–20).
- Author
-
Stimson, S., Evans, M., Hsu, C.-W., and Ng, C. Y.
- Subjects
PHOTOIONIZATION ,PHOTOELECTRONS ,SIMULATION methods & models ,VIBRATIONAL spectra ,QUANTUM theory ,IONS ,MOLECULAR dynamics - Abstract
The authors have obtained rotationally resolved vacuum ultraviolet pulsed field ionization-photoelectron (vuv-PFI-PE) spectrum of HD in the photon energy range of 15.29–18.11 eV, covering the ionization transitions HD
+ (X2 Σg + ,v+ =0–21,N+ )←HD(X1 Σg + ,v″ =0,J″ ). The assignment of rotational transitions resolved in the vuv-PFI-PE vibrational bands for HD+ (X2 Σg + ,v+ =0–20) and their simulation using the Buckingham-Orr-Sichel (BOS) model are presented. Rotational branches corresponding to the ΔN=N+ -J″ =0, ±1, ±2, ±3, and ±4 transitions are observed in the vuv-PFI-PE spectrum of HD. The BOS simulation shows that the perturbation of vuv-PFI-PE rotational line intensities due to near resonance autoionization is very minor at v+ >=5 and decreases as v+ is increased. Thus, the rotationally resolved PFI-PE bands for HD+ (v+ >=5) presented here provide reliable estimates of state-to-state cross sections for direct photoionization of HD, while the rotationally resolved PFI-PE bands for HD+ (v+ <5) are useful data for fundamental understanding of the near resonance autoionizing mechanism. On the basis of the rovibrational assignment of the vuv-PFI-PE bands, the ionization energies for the formation of HD+ (X2 Σg + ,v+ =0–20,N+ ) from HD(X1 Σg + ,v″ =0,J″ ) and the vibrational constants (ωe , ωe χe , ωe ye , and ωe ze ), the rotational constants (Be and αe ), the vibrational energy spacings, and the dissociation energy for HD+ (X2 Σg + ) are determined. As expected, these values are found to be in excellent agreement with high level theoretical predictions. [ABSTRACT FROM AUTHOR]- Published
- 2007
- Full Text
- View/download PDF