VIBFREQ1295: A New Database for Vibrational Frequency Calculations

• Published in: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Molecules, spectroscopy, kinetics, environment, & general theory, 2022-06, Vol.126 (25), p.4100-4122
• Main Authors: Zapata Trujillo, Juan C., McKemmish, Laura K.
• Format: Article
• Language: English
• Subjects: A: New Tools and Methods in Experiment and Theory
• ISSN: 1089-5639; 1520-5215
• DOI: 10.1021/acs.jpca.2c01438

High-throughput approaches for producing approximate vibrational spectral data for molecules of astrochemistry interest rely on harmonic frequency calculations using computational quantum chemistry. However, model chemistry recommendations (i.e., a level of theory and basis set pair) for these calculations are not yet available and, thus, thorough benchmarking against comprehensive benchmark databases is needed. Here, we present a new database for vibrational frequency calculations (VIBFREQ1295) storing 1295 experimental fundamental frequencies and CCSD­(T)­(F12*)/cc-pVDZ-F12 ab initio harmonic frequencies from 141 molecules. VIBFREQ1295’s experimental data was complied through a comprehensive review of contemporary experimental data, while the ab initio data was computed here. The chemical space spanned by the molecules chosen is considered in-depth and is shown to have good representation of common organic functional groups and vibrational modes. Scaling factors are routinely used to approximate the effect of anharmonicity and convert computed harmonic frequencies to predicted fundamental frequencies. With our experimental and high-level ab initio data, we find that a single global uniform scaling factor of 0.9617(3) results in median differences of 15.9(5) cm–1. A far superior performance with a median difference of 7.5(5) cm–1 can be obtained, however, by using separate scaling factors (SFs) for three regions: frequencies less than 1000 cm–1 (SF = 0.987(1)), between 1000 and 2000 cm–1 (SF = 0.9727(6)), and above 2000 cm–1 (SF = 0.9564(4)). This sets a lower bound for the performance that could be reliably obtained using scaling of harmonic frequency calculations to predict experimental fundamental frequencies. VIBFREQ1295’s most important purpose is to provide a robust database for benchmarking the performance of any vibrational frequency calculations. VIBFREQ1295 data could also be used to train machine-learning models for the prediction of vibrational spectra and as a reference and data starting point for more detailed spectroscopic modeling of particular molecules. The database can be found as part of the Supporting Information for this paper or in the Harvard DataVerse at https://doi.org/10.7910/DVN/VLVNU7.