Vibrational Stark Spectroscopy 3. Accurate Benchmark ab Initio and Density Functional Calculations for CO and CN

TLDR: In this article, a new Stark-type experimental technique known as electroabsorption spectroscopy has been developed in S. G. Boxer's laboratories which offers the ability to measure the responses of isotropic solvated molecules to an applied electric field.

Abstract: A new Stark-type experimental technique known as electroabsorption spectroscopy has been developed in S. G. Boxer's laboratories which offers the ability to measure the responses of isotropic solvated molecules to an applied electric field. It is applicable to a wide range of molecules and environments. We present benchmark ab initio and density-functional calculations employing 14 methods and double-ζ to penta-ζ augmented basis sets for the vibrational frequencies, dipole moment, polarizability, hyperpolarizability profiles, Stark shift, and other electroabsorption properties of two important (gas-phase) molecules, CO and CN-, for which a range of high-precision experimental data is available. The results show excellent agreement with these data, verify the earlier conclusion that the transition-moment polarizability rather than the polarizability change dominates the first-derivative response in the electroabsorption spectroscopy of these systems, and convergence with respect to the treatment of electro...