The dissociation of the2&Sgr;+gCO−2ions formed by electron attachment is studied with a classical trajectory method in which the initial conditions are represented by the Wigner probability density function and the electronic state2&Sgr;+gof CO−2is described by a Wall–Porter potential energy surface. Since both the ground initial state of CO2and the upper dissociative state of CO−2have an equilibrium angle of 180°, the dissociation is studied through the collinear approximation. The experimental data (excess energy transferred to vibration, population inversion of the vibrational CO levels) are found to be related not only to the autodetachment rate as usual, but also to some details of the repulsive potential energy surface such as the position and height of the saddlepoint and to the inertial coupling between translation and vibration.
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