Is explicitly correlated double-hybrid density functional theory advantageous for vibrational frequencies?

We have investigated the effect of F12 geminals on the basis set convergence of harmonic frequencies calculated using two representative double-hybrid density functionals, namely, B2GP-PLYP and revDSD-PBEP86-D4. Like previously found for energetics (Mehta N.; Martin J. M. L. J. Chem. Theory Comput. 2022, 18, 5978), one sees an acceleration by two zeta steps, such that even the cc-pVDZ-F12 basis set is quite close to the complete basis set (CBS) limit. However, the basis set convergence problem is not as acute as for energetics, and compared with experimental harmonic frequencies, conventional orbital calculations with augmented triple zeta quality basis set are acceptably close to the CBS limit, and can be carried out using analytical second derivatives. An efficient implementation of double-hybrid F12 analytical derivatives would make the F12 approach attractive in the sense that even an spd orbital basis set would be adequate. For the accurate revDSD-PBEP86-D4 functional, the role of differing local correlation terms (Perdew-Zunger 1981 versus VWN5) in different electronic structure programs has been investigated, while optimal double-hybrid parameters and performance statistics for energetics as well as frequencies differ slightly between the two implementations; these differences are insignificant for practical purposes.