Spin-Crossover from a Well-Behaved, Low-Cost meta-GGA Density Functional

Mejı́a-Rodrı́guez, Daniel; Trickey, S. B.

doi:10.1021/acs.jpca.0c08883

Cited by 25 publications

(41 citation statements)

References 50 publications

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“…Special care was taken to avoid numerical errors related to the numerical integration grid used in the DFT step that precedes RPA. It is known, for example, that the SCAN functional is sensitive to the density of points employed in numerical integration. − Throughout this work, we have used a fine grid of 150 radial and 590 spherical points. The grid was counterpoise-corrected within n -body fragments.…”

Section: Methodsmentioning

confidence: 99%

Random-Phase Approximation in Many-Body Noncovalent Systems: Methane in a Dodecahedral Water Cage

Modrzejewski

Yourdkhani

Śmiga

et al. 2021

J. Chem. Theory Comput.

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The many-body expansion (MBE) of energies of molecular clusters or solids offers a way to detect and analyze errors of theoretical methods that could go unnoticed if only the total energy of the system was considered. In this regard, the interaction between the methane molecule and its enclosing dodecahedral water cage, CH 4 •••(H 2 O) 20 , is a stringent test for approximate methods, including density functional theory (DFT) approximations. Hybrid and semilocal DFT approximations behave erratically for this system, with three-and four-body nonadditive terms having neither the correct sign nor magnitude. Here, we analyze to what extent these qualitative errors in different MBE contributions are conveyed to post-Kohn−Sham randomphase approximation (RPA), which uses approximate Kohn−Sham orbitals as its input. The results reveal a correlation between the quality of the DFT input states and the RPA results. Moreover, the renormalized singles energy (RSE) corrections play a crucial role in all orders of the many-body expansion. For dimers, RSE corrects the RPA underbinding for every tested Kohn−Sham model: generalized-gradient approximation (GGA), meta-GGA, (meta-)GGA hybrids, as well as the optimized effective potential at the correlated level. Remarkably, the inclusion of singles in RPA can also correct the wrong signs of three-and four-body nonadditive energies as well as mitigate the excessive higher-order contributions to the many-body expansion. The RPA errors are dominated by the contributions of compact clusters. As a workable method for large systems, we propose to replace those compact contributions with CCSD(T) energies and to sum up the remaining many-body contributions up to infinity with supermolecular or periodic RPA. As a demonstration of this approach, we show that for RPA(PBE0)+RSE it suffices to apply CCSD(T) to dimers and 30 compact, hydrogen-bonded trimers to get the methane−water cage interaction energy to within 1.6% of the reference value.

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Section: Methodsmentioning

confidence: 99%

Random-Phase Approximation in Many-Body Noncovalent Systems: Methane in a Dodecahedral Water Cage

Modrzejewski

Yourdkhani

Śmiga

et al. 2021

J. Chem. Theory Comput.

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“…21,24 Furthermore, r 2 SCAN also appears to be more accurate for complicated spin-crossover situations, even compared to its parent SCAN. 25 Since we place the focus of the new "3c" method on robustness and broad applicability, its less empirical nature has been central in the decision for r 2 SCAN over other very well performing mGGAs, such as GMTKN55 best-performers B97M-V and B97M-D4 26,27 (see also Section IV B). The new r 2 SCAN-3c composite scheme is developed along similar lines as all previous members of the series but involving the following conceptual and technical changes:…”

Section: Introductionmentioning

confidence: 99%

r2SCAN-3c: An Efficient “Swiss Army Knife” Composite Electronic-Structure Method

Hansen¹,

Ehlert²,

Mewes³

2020

Preprint

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The recently proposed second revision of the SCAN meta-GGA density-functional approximation (DFA) {Furness et al., J. Phys. Chem. Lett. 2020, 11, 8208-8215, termed r2SCAN} is used to construct an efficient composite electronic-structure method termed r2SCAN-3c, expanding the "3c'' series (hybrid: HSE/PBEh-3c, GGA: B97-3c, HF: HF-3c) to themGGA level. To this end, the unaltered r2SCAN functional is combined with a tailor-made triple-zeta Gaussian AO-basis as well as with refitted D4 and gCP corrections for London-dispersion and basis-set superposition error. The performance of the new method is evaluated for the GMTKN55 thermochemical database covering large parts of chemical space with about 1500 data points, as well as additional benchmarks for noncovalent interactions, organometallic reactions, lattice energies of organic molecules and ices, as well as for the adsorption on polar salt and non-polar coinage-metal surfaces. These comprehensive tests reveal a spectacular performance and robustness of r2SCAN-3c for reaction energies and noncovalent interactions in molecular and periodic systems, as well as outstanding conformational energies, and consistent structures. At just one tenth of the cost, r2SCAN-3c provides one of the best results of all semi-local DFT/QZ methods ever tested for the GMTKN55 benchmark database. Specifically for reaction and conformational energies as well as for noncovalent interactions, the new method outperforms hybrid-DFT/QZ approaches, compared to which the computational savings are even larger (factor 100-1000). In relation to other "3c'' methods, r2SCAN-3c by far surpasses the accuracy of its predecessor B97-3c at only about twice the cost. The perhaps most relevant remaining systematic deviation of r2SCAN-3c is due to self-interaction-error, owing to its mGGA nature. However, SIE is notably reduced compared to other (m)GGAs, as is demonstrated for several examples. After all, this remarkably efficient and robust method is chosen as our new group default, replacing previous low-level DFT and partially even expensive high-level methods in most standard applications for systems with up to several hundreds of atoms.

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“…The rSCAN meta-GGA 34 modifies SCAN to successfully improve numerical stability, but at the price of reduced accuracy [40][41][42] . To remove the divergence in the derivatives of α in single orbital regions (α → 0), 33 rSCAN uses a regularized α that breaks exact coordinate scaling conditions [43][44][45] and the uniform density limit obeyed by SCAN.…”

Section: Introductionmentioning

confidence: 99%

“…(A higher-order density-gradient expansion for exchange is recovered by SCAN 49 .) The satisfaction of exact constraints and greater smoothness of r 2 SCAN preserves the accuracy of SCAN and numerical efficiency of rSCAN 19,42,48,50 , permitting construction of meta-GGA pseudopotentials 51 . Therefore, we expect r 2 SCAN to be a better candidate for the rVV10 correction.…”

Section: Introductionmentioning

confidence: 99%

Workhorse minimally-empirical dispersion-corrected density functional, with tests for weakly-bound systems: r$^{2}$SCAN+rVV10

Ning¹,

Kothakonda²,

Furness³

et al. 2022

Preprint

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SCAN+rVV10 has been demonstrated to be a versatile van der Waals (vdW) density functional that delivers good predictions of both energetic and structural properties for many types of bonding. Recently, the r 2 SCAN functional has been devised as a revised form of SCAN with improved numerical stability. In this work, we refit the rVV10 functional to optimize the r 2 SCAN+rVV10 vdW density functional, and test its performance for molecular interactions and layered materials. Our molecular tests demonstrate that r 2 SCAN+rVV10 outperforms its predecessor SCAN+rVV10 in both efficiency (numerical stability) and accuracy. This good performance is also found in latticeconstant predictions. In comparison with benchmark results from higher-level theories or experiments, r 2 SCAN+rVV10 yields excellent interlayer binding energies and phonon dispersions for layered materials.

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Spin-Crossover from a Well-Behaved, Low-Cost meta-GGA Density Functional

Cited by 25 publications

References 50 publications

Random-Phase Approximation in Many-Body Noncovalent Systems: Methane in a Dodecahedral Water Cage

Random-Phase Approximation in Many-Body Noncovalent Systems: Methane in a Dodecahedral Water Cage

r2SCAN-3c: An Efficient “Swiss Army Knife” Composite Electronic-Structure Method

Workhorse minimally-empirical dispersion-corrected density functional, with tests for weakly-bound systems: r$^{2}$SCAN+rVV10

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