Is explicitly correlated double hybrid DFT advantageous for vibrational frequencies?

نویسندگان

چکیده

We have investigated the effect of F12 geminals on basis set convergence harmonic frequencies calculated using two representative double-hybrid density functionals, namely B2GP-PLYP and revDSD-PBEP86-D4. Like previously found for energetics [N. Mehta J. M. L. Martin, \textit{J. Chem. Theor. Comput.} \textbf{18}, 5978--5991 (2022)] one sees an acceleration by zeta steps, such that even cc-pVDZ-F12 is quite close to complete (CBS) limit. However, problem not as acute energetics, compared experimental frequencies, conventional orbital calculations with augmented triple quality are acceptably CBS limit, can be carried out analytical second derivatives. An efficient implementation double hybrid-F12 derivatives would make approach attractive in sense $spd$ adequate. For accurate revDSD-PBEP86-D4 functional, role differing local correlation terms (Perdew-Zunger 1981 vs. VWN5) different electronic structure programs has been investigated: while optimal hybrid parameters performance statistics well differ slightly between implementations, these differences insignificant practical purposes.

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ژورنال

عنوان ژورنال: Canadian Journal of Chemistry

سال: 2023

ISSN: ['0008-4042', '1480-3291']

DOI: https://doi.org/10.1139/cjc-2022-0277