The performance of explicitly correlated methods for the computation of anharmonic vibrational frequencies

Abstract

AbstractAnharmonic vibrational frequencies for closed‐shell molecules computed with CCSD(T)‐F12b/aug‐cc‐pVTZ differ from significantly more costly composite energy methods by a mean absolute error (MAE) of 7.5 cm−1 per fundamental frequency. Comparison to a few available gas phase experimental modes, however, actually lowers the MAE to 6.0 cm−1. Open‐shell molecules have an MAE of nearly a factor of six greater. Hence, open‐shell molecular anharmonic frequencies cannot be as well‐described with only explicitly correlated coupled cluster theory as their closed‐shell brethren. As a result, the use of quartic force fields and vibrational perturbation theory can be opened to molecules with six or more atoms, whereas previously such computations were limited to molecules of five or fewer atoms. This will certainly assist in studies of more chemically interesting species, especially for atmospheric and interstellar infrared spectroscopic characterization.