Computational vibrational spectroscopy for the detection of molecules in space

Abstract

Abstract Quartic force fields have been defining the potential portion of the internuclear Hamiltonian for decades. This review discusses the history of their development as a tool for analyzing and producing vibrational and rovibrational spectra for molecules of interest to astrophysical observation. Coupled cluster theory has long been a necessary partner in this development, and correlation consistent basis sets, second-order vibrational perturbation theory, and now explicitly correlated electronic wavefunctions have demonstrated consistent usefulness in the determination of these properties. The current status of this approach has produced vibrational frequencies within 1.0 cm−1 of experiment in many cases, preceded the laboratory observation of specific molecules, and is now becoming a helpful tool for the detection of new molecules in space.