Model Chemistry Recommendations for Scaled Harmonic Frequency Calculations: A Benchmark Study

Abstract

Despite the widespread popularity of scaled harmonic frequency calculations to predict experimental fundamental frequencies in chemistry, sparse benchmarking is available to guide users on the appropriate level of theory and basis set choices (model chemistry) or deep understanding of expected errors. An updated assessment of the best approach for scaling to minimize errors is also overdue. Here, we assess the performance of over 600 popular, contemporary, and robust model chemistries in the calculation of scaled harmonic frequencies, evaluating different scaling factor types and their implications in the scaled harmonic frequencies and model chemistry performance. We can summarize our results into three main findings: (1) Using model-chemistry-specific scaling factors optimized for three different frequency regions (low (<1,000 cm-1), mid (1,000-2,000 cm-1), and high (>2,000 cm-1)) results in substantial improvements in the agreement between the scaled harmonic and experimental frequencies compared to other choices. (2) Larger basis sets and more robust levels of theory generally lead to superior performance; however, the particular model chemistry choice matters and poor choices lead to significantly reduced accuracies. (3) Outliers are expected in routine calculations regardless of the model chemistry choice. Our benchmarking results here do not consider the intensity of vibrational transitions; however, we draw upon previous benchmarking results for dipole moments that highlight the importance of diffuse functions (i.e., augmented basis sets) in high-quality intensity predictions. In terms of specific recommendations, overall, the highest accuracy model chemistries are double-hybrid density functional approximations with a non-Pople augmented triple-ζ basis set, which can produce median frequency errors down to 7.6 cm-1 (DSD-PBEP86/def2-TZVPD), which is very close to the error in the harmonic approximation, i.e., the anharmonicity error. Double-ζ basis sets should not be used with double-hybrid functionals as there is no improvement compared to hybrid functional results (unlike for double-hybrid triple-ζ model chemistries). Note that 6-311G* and 6-311+G* basis sets perform like a double-ζ basis set for vibrational frequencies. After scaling, all studied hybrid functionals with non-Pople triple-ζ basis sets will produce median errors of less than 15 cm-1, with the best result of 9.9 cm-1 with B97-1/def2-TZVPD. Appropriate matching of double-ζ basis sets with hybrid functionals can produce high-quality results, but the precise choice of functional and basis set is more important. The B97-1, TPSS0-D3(BJ), or ωB97X-D hybrid density functionals with 6-31G*, pc-1, or pcseg-1 are recommended for fast routine calculations, all delivering median errors of 11-12 cm-1. Note that dispersion corrections are not easily available for B97-1; given its strong performance here, we recommend these be added to major programs in coming updates.