4.6 Article Proceedings Paper

Unimolecular and bimolecular reactions of state selected HCl+ ions formed via the R(1) pump line of the f (3)Delta(2) <- (1)Sigma(+) REMPI spectrum

Journal

PHYSICAL CHEMISTRY CHEMICAL PHYSICS
Volume 3, Issue 12, Pages 2253-2257

Publisher

ROYAL SOC CHEMISTRY
DOI: 10.1039/b009790j

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The properties of HCl+ ions formed in the vibronic ground state (2)Pi (3/2) (v = 0) via the R(1) pump line of the f(3)Delta (2) <-- (1)(+) REMPI Spectrum have been investigated. In the first experiment the rotational state distribution of these ions has been determined by photoexcitation into the A (2)Sigma (+)(v' = 7) state, which can predissociate. 73% of the HCl+ ions are found in the N = 0 state, 23% in the N = 1 and 4% in the N = 2 state. This experiment also yields the spectroscopic parameters of the A (2)Sigma (+)(v' = 7) State and information on the rotational dependence of the predissociation lifetimes of this state. The threshold for predissociation occurs between the N' = 0, J' = 1/2 and the N' = 1, J' = 1/2 state, leading to a new dissociation energy of the HCl+ ion of D-0 = 37 536.5 cm(-1) +/- 5 cm(-1). In the second experiment these state-selected HCl+ ions are investigated in an ion-molecule reaction with carbon monoxide. In this reaction very efficient proton transfer leads to the formation of HCO+ with a rate constant close to the Langevin limit.

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