Extrapolation in quantum chemistry: Insights on energetics and reaction dynamics

Abstract

Since there is no exact solution for problems in physics and chemistry, extrapolation methods may assume a key role in quantitative quantum chemistry. Two topics where it bears considerable impact are addressed, both at the heart of computational quantum chemistry: electronic structure and reaction dynamics. In the first, the problem of extrapolating the energy obtained by solving the electronic Schrödinger equation to the limit of the complete one-electron basis set is addressed. With the uniform-singlet-and-triplet-extrapolation (USTE) scheme at the focal point, the emphasis is on recent updates covering from the energy itself to other molecular properties. The second topic refers to extrapolation of quantum mechanical reactive scattering probabilities from zero total angular momentum to any of the values that it may assume when running quasiclassical trajectories, QCT/QM-[Formula: see text]J. With the extrapolation guided in both cases by physically motivated asymptotic theories, realism is seeked by avoiding unsecure jumps into the unknown. Although, mostly review oriented, a few issues are addressed for the first time here and there. Prospects for future work conclude the overview.