On Obtaining Reactive Potential Energy Surfaces from Transition State Photodetachment Spectra. I. Sensitivity Analysis

Abstract

We investigate the possibility of obtaining potential energy surfaces for chemical reactions from experimental photodetachment spectra by carrying out a sensitivity analysis. Specifically, the variations of the theoretical photodetachment spectrum with respect to the values of the potential on a grid of points (the “derivatives” of the spectrum) are calculated. We show how these derivatives can be obtained at no extra cost beyond that required to obtain the spectrum. Sensitivity analysis is performed on one- and two-degrees-of-freedom model photodetachment systems. The results are discussed in the context of the prospects for the “inversion” of transition state spectra to obtain potential surfaces in reactive systems.