The[Btilde]2A″2→[Xtilde]2E″ transition of 1,3,5-C6F3H3+and 1,3,5-C6F3D3+in discharge and supersonic free jet emission sources

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Abstract
Emission spectra of 1,3,5-C6F3H3 +(h 3 +) and 1,3,5-C6F3D3 +(d 3 +) ions were obtained by electron impact in seeded He and Ar supersonic free jets. The h 3 + (and d 3 +) spectra were recorded between 4570 (4445) Å and 4820 (4810) Å with a resolution R of the order of 0·5 cm-1. Gas phase discharge emission spectra of the same ions were photographed at R=0·25 cm-1 from 4450 to 4800 Å and R=0·1 cm-1, between 4500 and 4700 Å, and are compared to the jet cooled spectra. This comparison leads to some new or refined spectral assignments. Jet cooled and Ne matrix ion emission spectra are also compared, particularly with regard to frequencies and relative intensities of bands exhibiting the Jahn-Teller effect in the [Btilde] 2 A″2-[Xtilde] 2 E″ transition. Matrix dependent effects on Jahn-Teller levels and interaction parameters are observed and discussed. Rotational contour analysis of peak structures in the 00/0 and 61,1/2/0,0 emission bands in the discharge and jet spectra of the h 3 + ion indicates that ΔB ⋍ -0·0020 ± 0·0005 cm-1 and that the ground state Coriolis coefficients are ζ″0,1/2 ⋍ -0·8 to -0·6 and ζ″1,1/2 ⋍ -0·2 to +0·2. Possible consequences of spin-orbit interaction effects on the band contours are considered.