Abstract
The reaction of O(3 P) with COR m clusters to produce electronically excited CO2 was studied under molecular beam conditions. It was found that the spectrum of the chemiluminescence produced extended from the blue all the way to the near infrared. The dependence of the total emission intensity on stagnation pressure was investigated for (CO) m as well as for COR m , R=He, Ne, Ar, N2, CO2 and SO2. The low pressure data indicate that small (CO) m polymers are more efficient than clusters of CO with other species in inducing the chemiluminescent reaction. The larger CO-rare gas clusters, however, exhibited larger reaction cross-sections than those of the CO polymers. Rare gas clusters ofm≧5, on the other hand have successively smaller cross sections for reaction. The reactivity of the CO2 and SO2 clusters seems to peak at aboutm=1 and then decreases for larger species. An equilibrium model for cluster formation was proposed and it was found capable of explaining and simulating the experimental observations. Contrary to what was reported from afterglow experiments, no barrier for the reaction was detected.
Similar content being viewed by others
References
Nieman, J., Naaman, R.: Chem. Phys.90, 407 (1984)
Kondratiev, V.: Z. Phys.63, 322 (1930)
Gaydon, A.G.: Proc. R. Soc. London Ser. A176, 505 (1940)
Gaydon, A.G.: The spectroscopy of flames. Chap. 6. London: Chapman and Hall 1957
Clyne, M.A.A., Thrush, B.A.: Proc. R. Soc. London Ser. A269, 404 (1962)
Dixon, R.N.: Proc. R. Soc. London Ser. A275, 431 (1963)
Buck, U., Meyer, H.: Phys. Rev. Lett.52, 104 (1984)
Birkhofer, H.P., Haberland, H., Winterer, M., Worsnop, D.R.: Ber. Bunsenges. Phys. Chem.88, 207 (1984)
Andresen, P., Luntz, A.C.: J. Chem. Phys.72, 5842 (1980)
Toby, S., Ullrich, E.: Int. J. Chem. Kin.12, 535 (1980)
Kaufman, F.: In: Progress in reaction kinetics. Porter, G. (ed.), Vol. 1, p. 13. New York: Pergamon 1961
Hagena, O.: Surf. Sci.106, 101 (1981)
Hirschfelder, J.O., Curtis, C.F., Bird, R.B.: Molecular theory of gases and liquids. p. 1212. New York: Wiley 1954
Kassel, L.S.: Kinetics of homogeneous reactions. Chemical Catalog, N.Y. (1932)
Nieman, J., Naaman, R.: J. Chem. Phys. (in press)
Author information
Authors and Affiliations
Additional information
On leave from TRW Space and Technology Group, USA
Incumbent of the C.S. Koshland Career Development Chair