Photodissociation spectroscopy of the Ca+–N2 complex

The weakly bound complex Ca+–N2 is prepared in a pulsed nozzle/laser vaporization cluster source and studied with mass-selected photodissociation spectroscopy. The chromophore giving rise to the electronic transition is the 2P←2S atomic transition of Ca+. The appearance of spin–orbit doublets in the...

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Veröffentlicht in:The Journal of chemical physics 1998-02, Vol.108 (7), p.2725-2732
Hauptverfasser: Pullins, S. H., Reddic, J. E., France, M. R., Duncan, M. A.
Format: Artikel
Sprache:eng
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Zusammenfassung:The weakly bound complex Ca+–N2 is prepared in a pulsed nozzle/laser vaporization cluster source and studied with mass-selected photodissociation spectroscopy. The chromophore giving rise to the electronic transition is the 2P←2S atomic transition of Ca+. The appearance of spin–orbit doublets in the vibrationally resolved spectrum, as expected for a 2∏r←2∑+ transition, confirms that the complex is linear. The electronic transition in the complex lies to the red of the atomic resonance line indicating that the complex is more strongly bound in the excited state than in the ground state. The vibrationally resolved spectrum contains progressions in the Ca+–N2 stretching mode and in a combination of this stretch with the N–N stretch. Extrapolation of the Ca+–N2 stretch determines the excited state dissociation energy to be D0′=6500±500 cm−1, and an energetic cycle determines the ground state value to be D0″=1755±500 cm−1 (5.02 kcal/mol). The 2∏r(2,0,0)←2∑+(0,0,0) vibronic transition has been rotationally resolved yielding the bond lengths: rCaN=2.75 Å and rNN=1.15 Å for the 2∑+ ground state; rCaN=2.48 Å and rNN=1.17 Å for the 2∏ excited state.
ISSN:0021-9606
1089-7690
DOI:10.1063/1.475700