New Rydberg-Rydberg Transitions of the ArH and ArD Molecules. III. Emission from the 4 fComplexes
Abstract
We report observations and analyses of bands in the spectra of the ArH and ArD molecules due to emission from the 4fRydberg complexes. For ArD, the observed bands are 4f→ 5sand 4f→ 3dλ for all three components λ = 0, 1, and 2 of the 3dstate. These give direct information on all 14 spin-orbit components of the 4fcomplex. For ArH, the data is more limited because the levels of the 5sstate are broadened by predissociation, and only the λ = 2 component of the 4f→ 3dλ transitions is seen clearly, although a number of lines could be assigned to the 4f→ 3dπ band, which is strongly overlapped by the 6s→ 4pband. The 4fcomplexes of both isotopes are good example of Hund's case (d) coupling. The 4forbitals are essentially non-core-penetrating, so that spin-orbit coupling is negligible for them, and the zero-rotation splitting agrees well with calculations from the ab initio quadrupole moment and anisotropic polarizability of the core. The orbit-rotation coupling parameter ξ4fgives a value of the core electric dipole moment that is in reasonable agreement with ab initio and previous experimental values. A summary of the presently known states of ArH and ArD is presented.
- Publication:
-
Journal of Molecular Spectroscopy
- Pub Date:
- May 1998
- DOI:
- 10.1006/jmsp.1997.7524
- Bibcode:
- 1998JMoSp.189..110D