Vibrational state distributions of the SF−6+H, D→SF−5 +HF(v=0–12), DF(v=0–17) ion–molecule reactions are investigated with the flowing afterglow‐infrared chemiluminescence technique. The nascent distribution for the hydrogen reaction is (0.00)v=1 : (0.17)v=2 : (0.30)v=3 : (0.24)v=4 : (0.13)v=5 : (0.11)v=6 : (0.05)v=7 and for the deuterium reaction is (0.00)v=1 : (0.06)v=2 : (0.11)v=3 : (0.14)v=4 : (0.14)v=5 : (0.23)v=6 : (0.15)v=7 : (0.08)v=8 : (0.09)v=9. The fractions of the available energy deposited into the HF and DF vibrations are 0.37 and 0.38, respectively. The distributions do not show the characteristics of a statistical distribution that might be expected if a long‐lived complex occurs in the reaction. Instead, the distributions show a moderate amount of vibrational excitation due to an initial attractive energy release. Since the fraction of the available energy deposited into the diatomic vibration correlates well with the attractive energy release in L+HH′ systems, a larger fraction of the energy is released as repulsion during S–F bond scission, favoring product translation and SF−5 vibration. The collisions are most likely direct with negligible effects due to secondary encounters.
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1 March 1984
Research Article|
March 01 1984
Vibrational energy disposal in polyatomic ion–molecule reactions: SF−6+H, D→SF−5+HF(v), DF(v)
Charles E. Hamilton;
Charles E. Hamilton
Joint Institute for Laboratory Astrophysics, National Bureau of Standards and University of Colorado and Department of Chemistry, University of Colorado, Boulder, Colorado 80309
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Veronica M. Bierbaum;
Veronica M. Bierbaum
Joint Institute for Laboratory Astrophysics, National Bureau of Standards and University of Colorado and Department of Chemistry, University of Colorado, Boulder, Colorado 80309
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Stephen R. Leone
Stephen R. Leone
Joint Institute for Laboratory Astrophysics, National Bureau of Standards and University of Colorado and Department of Chemistry, University of Colorado, Boulder, Colorado 80309
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J. Chem. Phys. 80, 1831–1838 (1984)
Article history
Received:
October 12 1983
Accepted:
November 23 1983
Citation
Charles E. Hamilton, Veronica M. Bierbaum, Stephen R. Leone; Vibrational energy disposal in polyatomic ion–molecule reactions: SF−6+H, D→SF−5+HF(v), DF(v). J. Chem. Phys. 1 March 1984; 80 (5): 1831–1838. https://doi.org/10.1063/1.446942
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