Date Awarded


Document Type


Degree Name

Doctor of Philosophy (Ph.D.)




In this thesis a theory of associative detachment (A('-) + B (--->) AB + e) is presented. The theory is based on the close-coupling theory of Wang and Delos, but is more general in that final states of the nuclei (AB) are treated quantum mechanically. This is necessary since the molecule may be in any one of several vibrational states. The Schroedinger equation is reduced to an infinite set of coupled equations using carefully chosen assumptions. The coupled equations are uncoupled and the resulting equation for the wave function of the negative ion is solved to zero and first order. The first order solution is then used to find the wave function for the final states of the molecule. Two systems were examined: H (D) + Cl('-) and H (D) + F('-). In both cases the survival probability of the negative ion showed a striking isotope effect, with the survival probabilities found for D + Cl('-) and D + F('-) much smaller than those found for H + Cl('-) and H + F('-). Experimental rate constants were reproduced for H + Cl('-) and H + F('-).



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