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Studies in Hot Atom and Radiation Chemistry Progress Report: September 1977

Description: The reactive scattering of the reaction of the first excited state of C/sup +/ (/sup 4/P) with molecular hydrogen was studied over an energy range of 0.5 to 9.0 eV. The measurements indicate that the reaction proceeded by a direct mechanism and the final product was in the a/sup 3/pi state. The reaction of ground-state C/sup +/(/sup 2/P) with D/sub 2/ and H/sub 2/ was examined over the energy range of 2.5 eV to 28 eV. Over this energy range unambiguous identification of CD/sup +/ in the X/sup 1/sigma, a/sup 3/..pi.. and A/sup 1/..pi.. states was demonstrated. In addition the vibrational structure in the energy spectrum of CH/sup +/ and CD/sup +/ was resolved for the first time; the v = 0, 1, 2, and 3 product vibrational states were populated in the relative ratios 1.0:0.52:0.21:0.04. The vibrational band shapes permitted a determination of the rotational level distribution in the product. Careful measurements of the limiting value of the translational exoergicity (Q/sub MIN/) showed that the product state in the reaction F/sup +/(H/sub 2/,H)FH/sup +/ is /sup 2/..pi.. and that no FH/sup +/ in the /sup 2/sigma/sup +/ is formed although energetically feasible. Furthermore, it was shown that Q/sub MIN/ for the reactions of F/sup +/ with H/sub 2/ and D/sub 2/ were significantly lower than the values expected from known thermodynamic data. Experimental measurements coupled with quantum mechanical calculations showed that the displacement of Q/sub MIN/ in the reaction F/sup +/(H/sub 2/,H)FH/sup +/ and the corresponding deuterium analog relative to the thermodynamically expected value arises because of the presence of a dynamic rotational barrier in the potential energy curve. The reactions of Cl/sup +/(/sup 3/P,/sup 1/D) with D/sub 2/ were studied in the energy range 1 to 100 eV. Energy and angular distributions of the DCl/sup +/ ions were ...
Date: January 1, 1977
Creator: Koski, W. S.
Partner: UNT Libraries Government Documents Department