TITLE

Rotational population distribution of KH (v=0, 1, 2, and 3) in the reaction of K(5 2PJ, 6 2PJ, and 7 2PJ) with H2: Reaction mechanism and product energy disposal

AUTHOR(S)
Liu, Dean-Kuo; Lin, King-Chuen
PUB. DATE
November 1996
SOURCE
Journal of Chemical Physics;11/22/1996, Vol. 105 Issue 20, p9121
SOURCE TYPE
Academic Journal
DOC. TYPE
Article
ABSTRACT
Using a pump–probe method, we have systematically studied the rotational distribution of KH (v=0–3) produced in the reaction of K (5P, 6P, and 7P) with H2. The resulting rotational states fit roughly a statistical distribution at the system temperature, while the vibrational populations are characterized by a Boltzmann vibrational temperature of 1800, 3000, and 3100 K for the 5p, 6P, and 7P states, respectively. These results provide evidence that the reaction follows a collinear collisional geometry. This work has successfully probed KH from the K(5P) reaction, and confirms that a nonadiabatical transition via formation of an ion-pair K+H-2 intermediate should account for the reaction pathway. The available energy dissipation was measured to be (68±4)%, (26±2)%, and (6±3)% into the translation, vibration, and rotation of the KH product, respectively. The energy conversion into vibrational degree of freedom generally increases with the principal quantum number, indicating that the electron-jump distance elongates along the order of 5P<6P<7P. The result is different from the Cs(8P,9P)–H2 case, in which the electron-jump distances were considered roughly the same. Furthermore, a relatively large distance is expected to account for highly vibrational excitation found in the KH product. According to the classical trajectory computation reported by Polanyi and co-workers, the strong instability of the H-2 bond, inducing a large repulsion energy, appears to favor energy partitioning into the translation. © 1996 American Institute of Physics.
ACCESSION #
7639859

 

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