VIBRONIC EXCITATION IN $Na^{*} + Na_{2}$ COLLISIONS

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1981

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Ohio State University

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The system Na/Na/Na2/Na2 is encountered in alkali vapor lasers and sodium discharge lamps. Depending on the pressures of the constituents the overall process Na+Na2Na+Na2 may occur radiatively or collisonally [1]. We have modelled experimental data taken from [1], as well as data obtained in this laboratory, in order to elucidate (a) the relative contributions from radiative and collisional transfer and, more important, (b) the pattern of vibrational excitation in the Na2 (A) state consequent on collisional transfer between Na and Na2. So far as we are aware this is the first data on the latter point. Using a variety of models (the Golden Rule, ion-pair intermediates, the impulsive model, collision-complex) we have attempted to simulate the Na2 fluorescence spectrum recorded under conditions where collisional energy-transfer, $E\rightarrow $E,V, dominated [1]. In order to fit this spectrum we find we must invoke collisional transfer dynamics of a type which has been observed previously in some cases of pure EV transfer (rather than EE,V); in part the Na2 is excited resonantly to high v -levels of $Na_{2}^{*}$(A), and in part non-resonantly to low v -levels.

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[1] L. K. Lam, T. Fujimoto, A. C. Gallagher and M. M. Hessel: J. Chem. Phys., 68, 3553 (1978).


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