The photoexcitation spectra of transition region species in reactions of potassium + sodium halides (X = chlorine, bromine, iodine)
Barnes, Michael Dean
Brooks, Philip R.
Doctor of Philosophy
The photoexcitation spectra of transition region species formed in bimolecular reactions of K + NaX (X = Cl, Br, I) have been observed by measuring the intensity of sodium D line emission at 589.0 nm as a function of excitation wavelengths between 595 and 640 nm. The portion of the spectrum measured for the K + NaCl system is qualitatively similar to that previously observed by Magurie, et al (MAG86). The spectra obtained for the K + NaBr and NaI systems are significantly different than that of the K + NaCl system, and show a distinct feature centered at approximately 610 nm, and indicate that the reaction dynamics are quite different for the heavier sodium halide systems. The results of classical trajectory calculations performed using K + NaCl potential energy surfaces suggest that the structure in the K + NaBr and K + NaI spectra is not due to a mass effect; but rather from unique features of the potential energy surfaces for these reactions which are, as yet, unknown. Because of insufficient theoretical and experimental information, interpretation of these results in terms of the dynamical processes in these reactions is not yet possible. However, several different possible mechanisms of this structure are discussed which can be experimentally tested. Results of proposed future experiments should be able to provide the necessary information to understand the nature of these spectra.
Physical chemistry; Molecular physics