Sensitivity analysis in collinear reactive systems

Abstract

A sensitivity analysis formalism is constructed for collinear reactive systems with multiple electronic potential energy surfaces. The work extends the sphere of application of sensitivity theory into the reactive domain. Expressions are obtained for the first order elementary sensitivity coefficients (i.e. partial derivatives) of both the reactive and non-reactive component elements of the scattering matrix with respect to an arbitrary system parameter. In the case of the non-reactive elements, the sensitivity coefficients involve essentially the piecewise integration of a function matrix containing the available solution of the scattering problem. The reactive sensitivity coefficients draw on both forward and backward propagated solutions. The paper concludes with a discussion of the scope and applicability of reactive sensitivity analysis.