The regularized and restored semi-local meta-generalized gradient approximation (meta-GGA) exchange-correlation functional r2SCAN [Furness et al., J. Phys. Chem. Lett. 11, 8208-8215 (2020)] is used to create adiabatic-connection-derived global double-hybrid functionals employing spin-opposite-scaled MP2. The 0-DH, CIDH, QIDH, and 0-2 type double-hybrid functionals are assessed as a starting point for further modification. Variants with 50% and 69% Hartree-Fock exchange (HFX) are empirically optimized (Pr2SCAN50 and Pr2SCAN69), and the effect of MP2-regularization (κPr2SCAN50) and range-separated HFX (ωPr2SCAN50) is evaluated. All optimized functionals are combined with the state-of-the-art London dispersion corrections D4 and NL. The resulting functionals are assessed comprehensively for their performance on main-group and metal-organic thermochemistry on 90 different benchmark sets containing 25 800 data points. These include the extensive GMTKN55 database, additional sets for main-group chemistry, and multiple sets for transition-metal complexes, including the ROST61, the MOR41, and the MOBH35 sets. As the main target of this study is the development of a broadly applicable, robust functional with low empiricism, special focus is put on variants with moderate amounts of HFX (50%), which are compared to the so far successful PWPB95-D4 (50% HFX, 20% MP2 correlation) functional. The overall best variant, ωPr2SCAN50-D4, performs well on main-group and metal-organic thermochemistry, followed by Pr2SCAN69-D4 that offers a slight edge for metal-organic thermochemistry and by the low HFX global double-hybrid Pr2SCAN50-D4 that performs robustly across all tested sets. All four optimized functionals, Pr2SCAN69-D4, Pr2SCAN50-D4, κPr2SCAN50-D4, and ωPr2SCAN50-D4, outperform the PWPB95-D4 functional.
Download full-text PDF |
Source |
---|---|
http://dx.doi.org/10.1063/5.0174988 | DOI Listing |
Molecules
January 2025
Istituto di Biostrutture e Bioimmagini-CNR (IBB-CNR), Via De Amicis 95, I-80145 Napoli, Italy.
We perform DFT calculations with different hybrid (ωB97X-D and M05-2X) and double hybrid (B2PLYP-D3 and ωB2PLYP) functionals to characterize the lowest energy triplet excited states of naphthalene monomer and dimers in different stacking arrangements and to simulate their absorption spectra. We show that both excimer and localized triplet minima exist. In the former, the spin density is delocalized over the two monomers, adopting a face-to-face arrangement with a short inter-molecular distance.
View Article and Find Full Text PDFJ Phys Chem A
January 2025
INSTM, via G. Giusti 9, Firenze 50121, Italy.
The structures and rotational constants of prototypical monocyclic terpenes and terpenoids have been analyzed by a general computational strategy based on recent Pisa composite schemes (PCS) and vibrational perturbation theory at second order (VPT2). Concerning equilibrium geometries, a one-parameter empirical correction is added to bond lengths obtained by the revDSD-PBEP86 double hybrid functional in conjunction with a slightly modified cc-pVTZ-F12 basis set. The same functional and basis set give accurate harmonic frequencies, whereas the cheaper B3LYP hybrid functional in conjunction with a double-ζ basis set is employed to compute the semidiagonal cubic force constants needed to obtain vibrational corrections to the rotational constants in the framework of the VPT2 model.
View Article and Find Full Text PDFNat Comput Sci
December 2024
Department of Materials Science and Engineering, Massachusetts Institute of Technology, Cambridge, MA, USA.
Machine learning plays an important role in quantum chemistry, providing fast-to-evaluate predictive models for various properties of molecules; however, most existing machine learning models for molecular electronic properties use density functional theory (DFT) databases as ground truth in training, and their prediction accuracy cannot surpass that of DFT. In this work we developed a unified machine learning method for electronic structures of organic molecules using the gold-standard CCSD(T) calculations as training data. Tested on hydrocarbon molecules, our model outperforms DFT with several widely used hybrid and double-hybrid functionals in terms of both computational cost and prediction accuracy of various quantum chemical properties.
View Article and Find Full Text PDFJ Phys Chem A
December 2024
Department of Chemistry, University of the Free State, PO BOX 339, Bloemfontein 9300, South Africa.
Computational electronic structure methods, including ab initio and density functional theory (DFT), have been assessed in calculating the binding energies of 14 five-membered heterocyclic dimers. The configurations were generated using classical molecular dynamics before optimization at the MP2/aug-cc-pVTZ. Benchmark binding energies are calculated at the CCSD(T)/CBS level of theory.
View Article and Find Full Text PDFJ Comput Chem
January 2025
Manipal Centre for Natural Sciences, Manipal Academy of Higher Education, Manipal, Karnataka, India.
The magnetic nature of nonalternant hydrocarbon (Azulene) bridged nitronyl nitroxide (AzNN) and imino-nitroxide (AzIN) diradicals are investigated with 38 different DFT functionals to find out a correct functional to predict the magnetic nature of these diradicals. The effect of Hartree-Fock exchange (HFX) in the hybrid functionals are investigated for the prediction of magnetic nature of the nonalternant hydrocarbon bridged diradicals. The utility of Borden and Davidson's proposal of disjoint and nondisjoint SOMOs for the prediction of magnetic nature of alternant hydrocarbon bridged diradicals is assessed for the nonalternant hydrocarbon based diradicals.
View Article and Find Full Text PDFEnter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!