Exploring Avenues Beyond Revised DSD Functionals: II. Random-Phase Approximation and scaled MP3 corrections

Abstract

For revDSD double hybrids, the Görling-Levy second-order perturbation theory component is an Achilles' Heel when applied to systems with significant near-degeneracy ("static") correlation. We have explored its replacement by the direct random phase approximation (dRPA), inspired by the SCS-dRPA75 functional of Kállay and coworkers. The addition to the final energy of both a D4 empirical dispersion correction, and of a semilocal correlation component lead, to significant improvements, with DSD-PBEdRPA75-D4 approaching the performance of revDSD-PBEP86-D4 and the Berkeley $\omega$B97M(2). This form appears to be fairly insensitive to the choice of semilocal functional, but does exhibit stronger basis set sensitivity than the PT2-based double hybrids (due to much larger prefactors for the nonlocal correlation). As an alternative, we explored adding an MP3-like correction term (in a medium-sized basis sets) to a range-separated $\omega$DSD-PBEP86-D4 double hybrid, and found it to have significantly lower WTMAD2 (weighted mean absolute deviation) for the large and chemically diverse GMTKN55 benchmark suite; the added computational cost can be mitigated through density fitting techniques.

arXiv commentJ. Phys. Chem. A 125, ASAP (2021) Creative Commons License

References in corpus (16)

• Nonlocal van der Waals density functional: The simpler the better
• W4 theory for computational thermochemistry: in pursuit of confident sub-kJ/mol predictions
• The Ground State Correlation Energy of the Random Phase Approximation from a Ring Coupled Cluster Doubles Approach
• Empirical Double-Hybrid Density Functional Theory: A 'Third Way' In Between WFT and DFT
• SCAN-based hybrid and double-hybrid density functionals from models without fitted parameters
• Performance of ab initio and density functional methods for conformational equilibria of CnH2n+2 alkane isomers (n=2-8)
• Regularized Orbital-Optimized Second-Order Møller-Plesset Perturbation Theory: A Reliable Fifth-Order Scaling Electron Correlation Model with Orbital Energy Dependent Regularizers
• Particle-particle and quasiparticle random phase approximations: Connections to coupled cluster theory
• Systematically Improvable Tensor Hypercontraction: Interpolative Separable Density-Fitting for Molecules Applied to Exact Exchange, Second- and Third-Order Møller-Plesset Perturbation Theory
• ACCDB: A Collection of Chemistry DataBases for Broad Computational Purposes
• Performance of Localized Coupled Cluster Methods in a Moderately Strong Correlation Regime: Hückel-Möbius Interconversions in Expanded Porphyrins
• Third order Møller-Plesset theory made more useful? The role of density functional theory orbitals
• 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?
• Some Observations on the Performance of the Most Recent Exchange-Correlation Functionals for the Large and Chemically Diverse GMTKN55 Benchmark
• 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
• Probing the basis set limit for thermochemical contributions of inner-shell correlation: Balance of core-core and core-valence contributions

Cited by in corpus (4)

• 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
• Surprisingly Good Performance of XYG3 Family Functionals Using Scaled KS-MP3 Correlation
• Performance of Localized-Orbital Coupled Cluster Approaches for the Conformational Energies of Longer n-alkane Chains