Performance of Minnesota Functionals on Vibrational Frequency

Abstract

ABSTRACTMolecular geometry and harmonic frequency calculations are essential in thermochemical computations, with density functional theory (DFT) being widely employed for vibrational frequency predictions due to its efficiency and accuracy. In this study, we assessed the precision of 28 Minnesota based functionals with three different basis sets using the VIBFREQ1295 dataset. Scaling factors are necessary for predicting fundamental frequencies, global scaling factors were fitted by using F38/10 and VIBFREQ1295 datasets. The superior performing functionals were then fitted based on vibrational frequency ranges to obtain frequency‐range‐specific scaling factors. We observed consistent outlier across various model chemistries in vibrational frequency predictions, with alternative scaling factors showing minimal impact on reducing outlier occurrences. Besides, large basis sets are not indispensably required for fundamental frequency predictions. M06‐L, revM06‐L, SOGGA11‐X, PW6B95‐D3(BJ), CF22D, and M06‐2X consistently exhibit excellent performance across the three basis sets. When using frequency‐range‐specific scaling factors, the root mean squard errors (RMSEs) and median absolute errors (MedAEs) of almost all the selected functionals were reduced. PW6B95‐D3(BJ), CF22D, and MN12‐SX exhibited the lowest RMSEs. Comparisons were also done for different data classifications; the dataset was classified by the elements of the molecules, vibrational frequency intervals, and vibrational modes.