On Obtaining Reactive Potential Energy Surfaces from Transition State Photodetachment Spectra. II. Inversion of Spectra in Model Systems

We present a method for determining reactive potential energy surfaces from experimental photodetachment spectra. The variations of the theoretical photodetachment spectrum with respect to potential parameters (the "derivatives" of the spectrum) are calculated. These derivatives are used in an iterative Levenberg-Marquardt-based algorithm to find the optimal values of the potential parameters, i.e., those yielding the theoretical spectrum that best matches the experimental one. Applications of the method to one- and two-degrees-of-freedom model systems are presented, and accurate results are obtained with a small number of iterations. Prospects for treating realistic systems are discussed.