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Kinetic-energy dependence of competitive spin-allowed and spin-forbidden reactions: V++CS2
- Source :
- ResearcherID
- Publication Year :
- 1999
- Publisher :
- AIP Publishing, 1999.
-
Abstract
- The kinetic-energy dependence of the V++CS2 reaction is examined using guided ion-beam mass spectrometry. Several different ion sources are used to systematically vary the V+ electronic state distributions and elucidate the reactivities of both the ground and excited state V+ cation. The cross section for VS+ formation from ground state V+(5D) exhibits two endothermic features corresponding to the formation of ground state VS+(3Σ−) and excited state VS+(5Π). The thresholds for these two processes are in good agreement with theoretically determined excitation energies. The cross section for spin-forbidden formation of ground state VS+(3Σ−) exhibits an unusual variation with kinetic energy that is attributed to the energy dependence of the surface-crossing probability. From the thresholds associated with the formation of VS+ and V(CS)+, D0(V+–S)=3.72±0.09 eV and D0(V+–CS)=1.70±0.08 eV are derived. Further, circumstantial evidence for formation of a high-energy isomer of V(CS)+ is obtained.
Details
- ISSN :
- 10897690 and 00219606
- Volume :
- 110
- Database :
- OpenAIRE
- Journal :
- The Journal of Chemical Physics
- Accession number :
- edsair.doi.dedup.....59d7849c21adf322aa2e31c5942cf815