Comprehensive Assessment of GFN Tight-Binding and Composite Density Functional Theory Methods for Calculating...

Vibrational spectroscopy is a valuable and widely used analytical tool for the characterization of chemical substances. We investigate the performance of semiempirical quantum mechanical GFN tight-binding and force-field methods for the calculation of gas-phase infrared spectra in comparison to experiment and low-cost (B3LYP-3c) density functional theory. A data set of 7247 experimental references was used to evaluate method performance based on automatic spectra comparison. Various quantitative spectral similarity measures were employed for the comparison between theory and experiment and for determining empirical scaling factors. It is shown that the scaling of atomic masses provides an accurate yet simple alternative to standard global frequency scaling in density functional theory (DFT) and semiempirical calculations. Furthermore, the method performance for 58 exemplary transition metal complexes was investigated. The efficient DFT composite method B3LYP-3c, that was introduced in the course of this work, was found to be excellently suited for general IR spectra calculations. The GFN1- and GFN2-xTB tight-binding methods clearly outperformed the PMx competitors. Conformational changes were investigated for a subset of the data and are found to have a mediocre strong influence on the simulated spectra suggesting that the corresponding elaborate sampling steps may be neglected in automated compound identification workflows.