Journal
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
Volume 12, Issue 40, Pages 13091-13098Publisher
ROYAL SOC CHEMISTRY
DOI: 10.1039/c0cp00537a
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Funding
- NASA
- National Science Foundation [CHE-0647088]
- NSF through NCSA
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Experimental studies of gas phase reactions of carbanions with N and O atoms have been reported previously to understand ion chemistry relevant to the interstellar medium. In all cases reactions of anions with O atoms exhibit larger reaction rate constants compared to the corresponding N atom reactions. In addition, the open-shell carbon chain anions exhibit higher reactivities than the corresponding closed-shell species in N atom reactions, whereas similar reactivities were observed for both open and closed-shell anions in O atom reactions. These trends are investigated by the current theoretical study of the reactions of HCn(-)(n = 2, 4, and 6) and Cn(-)(n = 2, 4-7) with N and O atoms. Our results indicate that spin-forbidden processes are the probable pathways in reactions of closed-shell anions HCn(-) with N atoms, and spin conversion limits the reaction efficiency. In reactions of open-shell anions Cn(-) with N atoms, about 50% of the collisions may proceed through spin-allowed barrierless pathways, which results in relatively higher reaction efficiencies than for the closed-shell reactions. For reactions of all anions with O atoms, the spin-allowed barrierless pathways are the only channels, such that all reactions occur with very high efficiencies. This work provides a greater understanding of the influence of spin effects on the reactivities of anion reactions involving N and O atoms that may be important in the interstellar medium.
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