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

TL;DR

This benchmark study evaluates over 600 model chemistries for scaled harmonic frequency calculations, providing specific recommendations for optimal levels of theory and basis sets to improve accuracy in vibrational frequency predictions.

Contribution

It offers the first comprehensive benchmarking of model chemistries for scaled harmonic frequency calculations, guiding users on optimal choices for different frequency regions.

Findings

Model chemistry-specific scaling factors improve accuracy.

Larger basis sets and robust theories generally perform better.

Outliers are common in routine calculations.

Abstract

Despite the popularity of scaled harmonic frequency calculations in chemistry, sparse benchmarking is available to guide users on appropriate level of theory and basis set choices (model chemistry). Here, we assess the performance of over 600 model chemistries in scaled harmonic frequencies calculations evaluating different scaling factors types. We can summarise our results into three main findings: (1) using model chemistry-specific scaling factors optimised for three different frequency regions (low (below 1,000cm-1), mid (1,000-2,000cm-1), and high (above 2,000cm-1)) results in better 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 (3) outliers should be expected in routine calculations. In terms of specific recommendations, overall, the highest accuracy model chemistries are double-hybrid functionals with non-Pople augmented triple-zeta basis sets, which can produce median frequency errors of down to 7.6cm-1 (DSD-PBEP86/def2-TZVPD) lying close to the error in the harmonic approximation. Double-zeta basis sets should not be used with double-hybrid functionals as there is no improvement compared to hybrid functionals. Note that the 6-311G* and 6-311+G* bases perform like double-zeta basis sets for vibrational frequencies. After scaling, all studied hybrid functionals with non-Pople triple-zeta basis sets will produce median errors of less than 15cm-1, with the best result of 9.9cm-1 with B97-1/def2-TZVPD. Appropriate matching of double-zeta basis sets with hybrid functionals can produce high quality results. The B97-1, TPSS0-D3(BJ) or wB97X-D hybrid functionals with 6-31G*, pc-1 or pcseg-1 are recommended for fast routine calculations, all delivering median errors of 11-12cm-1.