Angular scattering using parameterized Smatrix elements for the H + D2(vi = 0, ji = 0) → HD(vf = 3, jf = 0) + D reaction: an example of Heisenberg's Smatrix programme

Abstract

A neglected topic in the theory of reactive scattering is the use of parameterized scattering (S) matrix elements to calculate differential cross sections (DCSs). We construct four simple parameterizations, whose moduli are smooth step-functions and whose phases are quadratic functions of the total angular momentum quantum number. Application is made to forward glory scattering in the DCS of the H + D₂(v_i = 0, j_i = 0) → HD(v_f = 3, j_f = 0) + D reaction at a translational energy of 1.81 eV, where v and j are vibrational and rotational quantum numbers respectively. The parameterized S matrix elements can reproduce the forward scattering for centre-of-mass reactive scattering angles up to 30° and can identify the total angular momenta (equivalently, impact parameters) that contribute to the glory. The theoretical techniques employed to analyze structure in the DCS include: nearside–farside theory, local angular momentum theory—in both cases incorporating resummations of the partial wave series representation of the scattering amplitude—and the uniform semiclassical theory of forward glory scattering. Our approach is an example of Heisenberg's S matrix programme, in which no potential energy surface is used. Our calculations for the DCS using the four parameterized S matrix elements are counterexamples to the following universal statements often found in the chemical physics literature: “every molecular scattering investigation needs detailed information about the interaction potential,” and “an accurate potential energy surface is an essential element in carrying out simulations of a chemical reaction”. Both these statements are false.