Can G4-like Composite Ab Initio Methods Accurately Predict Vibrational Harmonic Frequencies?

TL;DR

This study evaluates the accuracy of G4-like composite ab initio methods in predicting vibrational harmonic frequencies, demonstrating their high accuracy and cost-effectiveness compared to traditional methods, especially with ANO basis sets.

Contribution

It provides a comprehensive validation of G4-like composite methods for vibrational frequencies against experimental data, highlighting their advantages with ANO basis sets.

Findings

G4-T is three times more accurate than CCSD(T)/def2-TZVP.

G4-T_ano is twice as accurate as CCSD(T)/ano-pVTZ.

Composite schemes with ANO basis sets achieve ~5 cm^{-1} RMS deviation.

Abstract

Minimally empirical G4-like composite wavefunction theories [E. Semidalas and J. M. L. Martin, \textit{J. Chem. Theory Comput.} {\bf 16}, 4238-4255 and 7507-7524 (2020)] trained against the large and chemically diverse GMTKN55 benchmark suite have demonstrated both accuracy and cost-effectiveness in predicting thermochemistry, barrier heights, and noncovalent interaction energies. Here, we assess the spectroscopic accuracy of top-performing methods: G4-\textit{n}, cc-G4-\textit{n}, and G4-\textit{n}-F12, and validate them against explicitly correlated coupled cluster CCSD(T*)(F12*) harmonic vibrational frequencies and experimental data from the HFREQ2014 dataset, of small first- and second-row polyatomics. G4-T is three times more accurate than plain CCSD(T)/def2-TZVP, while G4-T$_{\rm ano}$ is two times superior to CCSD(T)/ano-pVTZ. Combining CCSD(T)/ano-pVTZ with MP2-F12 in a parameter-free composite scheme results to a root-mean-square deviation of ~5 cm$^{-1}$ relative to experiment, comparable to CCSD(T) at the complete basis set limit. Application to the harmonic frequencies of benzene reveals a significant advantage of composites with ANO basis sets -- MP2/ano-pV\textit{m}Z and [CCSD(T)-MP2]/ano-pVTZ (\textit{m} = Q or 5) -- over similar protocols based on CCSD(T)/def2-TZVP. Overall, G4-type composite energy schemes, particularly when combined with ANO basis sets in CCSD(T), are accurate and comparatively inexpensive tools for computational vibrational spectroscopy.