ISSN:
1089-7690
Source:
AIP Digital Archive
Topics:
Physics
,
Chemistry and Pharmacology
Notes:
Optical spectra of ten AX+ ions (A=B, Al, Ga, In; X=F, Cl, Br) have been observed in the visible and near UV; a total of 18 band systems were newly discovered. The emission was produced by chemiluminescent reactions A++X2 at low (2–10 eVCM) kinetic energy in a beam-gas arrangement. A position-sensitive photon counting detector with large surface area and very low dark count rate was employed, the resolution was mostly 5–50 A(ring) FWHM. Three types of band systems were observed: (1) For all AX+ combinations except BCl+ and BBr+, a very broad quasicontinuum with undulatory structure appears. On the basis of electronic state correlation arguments, photoelectron data, some ab initio calculations and, in one case, a known emission spectrum (InCl+) these band systems were identified as B 2Σ+–X 2Σ+ transitions. It is concluded that the excited state potentials are considerably displaced against the ground state, and their energetics are given. (2) For six species AX+, narrow band systems were observed in the 2500 A(ring) region. They could be clearly identified as being due to C 2Π–X 2Σ+ transitions by means of comparison with the systematics of the analogous A 2Π–X 2Σ+ transitions of the isoelectronic alkaline earth halides, by the resolved fine structure, and, in the case of AlF+, by an ab initio calculation. (3) In the GaCl+, GaBr+, and InBr+ spectra, narrow features accompany the C–X transitions. They are attributed to D 2Σ+–X 2Σ+ transitions, analogous to the alkaline earth halide B 2Σ+–X 2Σ+ band systems. Qualitative electronic state correlations are discussed, and the expected dominant configurations in different regions of the AX+ ground and excited states are given. These are in accord with recent ab initio results on AlF+.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1063/1.455290
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