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Kinetic-energy dependence of competitive spin-allowed and spin-forbidden reactions: V++CS2

Authors :
Helmut Schwarz
Chad Rue
Ilona Kretzschmar
Detlef Schröder
P. B. Armentrout
Jeremy N. Harvey
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