Harmonic Scale Factors of Fundamental Transitions for Dispersion‐corrected Quantum Chemical Methods

Abstract

This work provides a procedure and database for obtaining the vibrational frequency scale factors that align quantum chemically computed harmonic frequencies with experimental vibrational spectroscopic data. The database comprises 441 molecules of various sizes, from diatomics to the buckminsterfullerene C60. We provide scale factors for 27 dispersion‐corrected methods, 24 of which are DF‐Dn/B with DF=BLYP, PBE, B3LYP, PBE0, Dn=D3(BJ), D4, and B=6‐31G, def2‐SVP, def2‐TZVP, and three of them are the 3c‐family composite methods (HF‐3c, PBEh‐3c, and r2$SCAN‐3c). The two scale factors are derived for each method: the absolute scaling, minimizing the absolute deviation of the scaled harmonic frequency from the experimental value, and the relative scaling, which minimizes an analogous relative deviation. The absolute type of scaling is recommended for frequencies above 2000 cm‐1, while the relative scaling is optimal for frequencies below 2000 cm‐1.