Canonical and DLPNO-based composite wavefunction methods parametrized against large and chemically diverse training sets. 2. Correlation consistent basis sets, core-valence correlation, and F12 alternatives

Abstract

A hierarchy of wavefunction composite methods (cWFT), based on G4- type cWFT methods available for elements H through Rn, was recently reported by Semidalas and Martin [J. Chem. Theor. Comput. 2020, 16, 4238]. We extend this hierarchy by considering the inner-shell correlation energy in the second-order Moller-Plesset correction and replacing the Weigend-Ahlrichs def2-mZVPP(D) basis sets used in the aforementioned paper with complete basis set extrapolation from augmented correlation consistent core-valence triple-zeta, aug-cc-pwCVTZ(-PP), and quadruple-zeta, aug-cc-pwCVQZ(-PP), basis sets, thus creating cc-G4- type methods. For the large and chemically diverse GMTKN55 benchmark suite, they represent a substantial further improvement and bring WTMAD2 (weighted mean absolute deviation) down below 1 kcal/mol. Intriguingly, the lion's share of the improvement comes from better capture of valence correlation; the inclusion of core-valence correlation is almost an order of magnitude less important. These robust correlation consistent cWFT methods approach the CCSD(T) complete basis limit with just one or a few fitted parameters. Particularly the DLPNO variants such as cc-G4-T-DLPNO are applicable to fairly large molecules at modest computational cost, as is (for a reduced range of elements) a different variant using MP2-F12/cc-pVTZ-F12 for the MP2 component.

arXiv commentJ. Chem. Theor. Comput., ASAP (Open Access under CC)

References in corpus (14)

• Development of Novel Density Functionals for Thermochemical Kinetics
• Correlation consistent valence basis sets for use with the Stuttgart-Dresden-Bonn relativistic effective core potentials: the atoms Ga-Kr and In-Xe
• Towards standard methods for benchmark quality ab initio thermochemistry --- W1 and W2 theory
• W4 theory for computational thermochemistry: in pursuit of confident sub-kJ/mol predictions
• Assessment of W1 and W2 theories for the computation of electron affinities, ionization potentials, heats of formation, and proton affinities
• Empirical Double-Hybrid Density Functional Theory: A 'Third Way' In Between WFT and DFT
• Basis set convergence of post-CCSD contributions to molecular atomization energies
• Toward a W4-F12 approach: Can explicitly correlated and orbital-based ab initio CCSD(T) limits be reconciled?
• ACCDB: A Collection of Chemistry DataBases for Broad Computational Purposes
• Do CCSD and approximate CCSD-F12 variants converge to the same basis set limits? The case of atomization energies
• Canonical and DLPNO-based G4(MP2)XK-inspired composite wavefunction methods parametrized against large and chemically diverse training sets: Are they more accurate and/or robust than double hybrid DFT?
• A Simple 'Range Extender' for Basis Set Extrapolation Methods for MP2 and Coupled Cluster Correlation Energies
• Probing the basis set limit for thermochemical contributions of inner-shell correlation: Balance of core-core and core-valence contributions
• A Simple Model For Scalar Relativistic Corrections To Molecular Total Atomization Energies

Cited by in corpus (8)

• Exploring Avenues Beyond Revised DSD Functionals: I. range separation, with xDSD as a special case
• The MOBH35 metal-organic barrier heights reconsidered: performance of local-orbital coupled cluster approaches in different static correlation regimes
• Explicitly correlated double hybrid DFT: a comprehensive analysis of the basis set convergence on the GMTKN55 database
• W4$\Lambda$: leveraging $\Lambda$ coupled cluster for accurate computational thermochemistry approaches
• Exploring Avenues Beyond Revised DSD Functionals: II. Random-Phase Approximation and scaled MP3 corrections
• Surprisingly Good Performance of XYG3 Family Functionals Using Scaled KS-MP3 Correlation
• Can G4-like Composite Ab Initio Methods Accurately Predict Vibrational Harmonic Frequencies?
• The S66 Noncovalent Interaction Benchmark Re-examined: Composite Localized Coupled Cluster Approaches