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Accuracy Meets Interpretability for Computational Spectroscopy by Means of Hybrid and Double-Hybrid Functionals.

ABSTRACT: Accuracy and interpretability are often seen as the devil and holy grail in computational spectroscopy and their reconciliation remains a primary research goal. In the last few decades, density functional theory has revolutionized the situation, paving the way to reliable yet effective models for medium size molecules, which could also be profitably used by non-specialists. In this contribution we will compare the results of some widely used hybrid and double hybrid functionals with the aim of defining the most suitable recipe for all the spectroscopic parameters of interest in rotational and vibrational spectroscopy, going beyond the rigid rotor/harmonic oscillator model. We will show that last-generation hybrid and double hybrid functionals in conjunction with partially augmented double- and triple-zeta basis sets can offer, in the framework of second order vibrational perturbation theory, a general, robust, and user-friendly tool with unprecedented accuracy for medium-size semi-rigid molecules.

SUBMITTER: Barone V

PROVIDER: S-EPMC7645164 | biostudies-literature | 2020

REPOSITORIES: biostudies-literature

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Accuracy Meets Interpretability for Computational Spectroscopy by Means of Hybrid and Double-Hybrid Functionals.

Barone Vincenzo V Ceselin Giorgia G Fusè Marco M Tasinato Nicola N

Frontiers in chemistry 20201023

Accuracy and interpretability are often seen as the devil and holy grail in computational spectroscopy and their reconciliation remains a primary research goal. In the last few decades, density functional theory has revolutionized the situation, paving the way to reliable yet effective models for medium size molecules, which could also be profitably used by non-specialists. In this contribution we will compare the results of some widely used hybrid and double hybrid functionals with the aim of d ...[more]

PMID: 33195078

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Project description:We present a family of minimally empirical double-hybrid DFT functionals parametrized against the very large and diverse GMTKN55 benchmark. The very recently proposed ωB97M(2) empirical double hybrid (with 16 adjustable parameters) has the lowest WTMAD2 (weighted mean absolute deviation over GMTKN55) ever reported at 2.19 kcal/mol. However, refits of the DSD-BLYP and DSD-PBEP86 spin-component-scaled, dispersion-corrected double hybrids can achieve WTMAD2 values as low as 2.33 with the very recent D4 dispersion correction (2.42 kcal/mol with the D3(BJ) dispersion term) using just a handful of adjustable parameters. If we use full DFT correlation in the initial orbital evaluation, the xrevDSD-PBEP86-D4 functional reaches WTMAD2 = 2.23 kcal/mol, statistically indistinguishable from ωB97M(2) but using just four nonarbitrary adjustable parameters (and three semiarbitrary ones). The changes from the original DSD parametrizations are primarily due to noncovalent interaction energies for large systems, which were undersampled in the original parametrization set. With the new parametrization, same-spin correlation can be eliminated at minimal cost in performance, which permits revDOD-PBEP86-D4 and revDOD-PBE-D4 functionals that scale as N4 or even N3 with the size of the system. Dependence of WTMAD2 for DSD functionals on the percentage of HF exchange is roughly quadratic; it is sufficiently weak that any reasonable value in the 64% to 72% range can be chosen semiarbitrarily. DSD-SCAN and DOD-SCAN double hybrids involving the SCAN nonempirical meta-GGA as the semilocal component have also been considered and offer a good alternative if one wishes to eliminate either the empirical dispersion correction or the same-spin correlation component. noDispSD-SCAN66 achieves WTMAD2 = 3.0 kcal/mol, compared to 2.7 kcal/mol for DOD-SCAN66-D4. However, the best performance without dispersion corrections (WTMAD2 = 2.8 kcal/mol) is reached by revωB97X-2, a slight reparametrization of the Chai-Head-Gordon range-separated double hybrid. Finally, in the context of double-hybrid functionals, the very recent D4 dispersion correction is clearly superior over D3(BJ).

Dataset Information

Accuracy Meets Interpretability for Computational Spectroscopy by Means of Hybrid and Double-Hybrid Functionals.

Publications

Accuracy Meets Interpretability for Computational Spectroscopy by Means of Hybrid and Double-Hybrid Functionals.

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