On the performance of various hierarchized bases in extrapolating the correlation energy to the complete basis set limit

Pansini, F.N.N.; Neto, A. Canal; Varandas, A. J. C.

doi:10.1016/j.cplett.2015.10.064

Cited by 29 publications

(17 citation statements)

References 42 publications

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“…Regarding E CAS ∞ , values from Equation 3 with the (6, 7) cardinal pair (15, 136, 137) andβ = 1.26 (81) were used. Specific x-numbers were then obtained as averages of homologs so calculated for the 18-system set (89,90,108). Because they should be close to the associated cardinals (90, 108), x k was constrained to minimize the RMSD between the two, with the search carried out (92) near x k = 7 for the grid 1.2 ≤β ≤ 2.0 and 6.50 ≤ x k ≤ 7.50.…”

Section: Complete Basis Set Extrapolation Of Hartree-fock-like Energimentioning

confidence: 99%

Straightening the Hierarchical Staircase for Basis Set Extrapolations: A Low-Cost Approach to High-Accuracy Computational Chemistry

Varandas

2018

Annu. Rev. Phys. Chem.

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Because the one-electron basis set limit is difficult to reach in correlated post-Hartree-Fock ab initio calculations, the low-cost route of using methods that extrapolate to the estimated basis set limit attracts immediate interest. The situation is somewhat more satisfactory at the Hartree-Fock level because numerical calculation of the energy is often affordable at nearly converged basis set levels. Still, extrapolation schemes for the Hartree-Fock energy are addressed here, although the focus is on the more slowly convergent and computationally demanding correlation energy. Because they are frequently based on the gold-standard coupled-cluster theory with single, double, and perturbative triple excitations [CCSD(T)], correlated calculations are often affordable only with the smallest basis sets, and hence single-level extrapolations from one raw energy could attain maximum usefulness. This possibility is examined. Whenever possible, this review uses raw data from second-order Møller-Plesset perturbation theory, as well as CCSD, CCSD(T), and multireference configuration interaction methods. Inescapably, the emphasis is on work done by the author's research group. Certain issues in need of further research or review are pinpointed.

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Section: Complete Basis Set Extrapolation Of Hartree-fock-like Energimentioning

confidence: 99%

Straightening the Hierarchical Staircase for Basis Set Extrapolations: A Low-Cost Approach to High-Accuracy Computational Chemistry

Varandas

2018

Annu. Rev. Phys. Chem.

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“…* the correlation energy obtained from the two-point extrapolation scheme USTE(x-1,x) of Varandas and co-workers: [90] E corr…”

Section: Quantum Chemical Calculationsmentioning

confidence: 99%

On the Interplay between Charge‐Shift Bonding and Halogen Bonding

et al. 2020

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The nature of halogen-bond interactions has been analysed from the perspective of the astatine element, which is potentially the strongest halogen-bond donor. Relativistic quantum calculations on complexes formed between halide anions and a series of Y 3 CÀ X (Y=F to X, X=I, At) halogen-bond donors disclosed unexpected trends, e. g., At 3 CÀ At revealing a weaker donating ability than I 3 CÀ I despite a stronger polarizability. All the observed peculiarities have their origin in a specific component of CÀ Y bonds: the charge-shift bonding.Descriptors of the Quantum Chemical Topology show that the halogen-bond strength can be quantitatively anticipated from the magnitude of charge-shift bonding operating in Y 3 CÀ X. The charge-shift mechanism weakens the ability of the halogen atom X to engage in halogen bonds. This outcome provides rationales for outlier halogen-bond complexes, which are at variance with the consensus that the halogen-bond strength scales with the polarizability of the halogen atom.

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“…and co-workers. 2,34,35,36,37,38,39,40,41,42,43,44,45,46,47,48,49,50,51,52,53,54,55,56 Owing to the systematic convergence of these basis sets, basis set extrapolations are an effective approach for converging the n-particle space while keeping the computational cost at a minimum. However, the optimal extrapolation parameters may depend on the correlation component being extrapolated (e.g., CCSD or (T)) and the specific basis sets being used in the extrapolation.…”

Section: Introductionmentioning

confidence: 99%

Effective basis set extrapolations for CCSDT, CCSDT(Q), and CCSDTQ correlation energies

Karton

2020

The Journal of Chemical Physics

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It is well established that extrapolating the CCSD and (T) correlation energies using empirically motivated extrapolation exponents can accelerate the basis set convergence. Here we consider the extrapolation of coupled-cluster expansion terms beyond the CCSD(T) level to the complete basis set (CBS) limit. We obtain reference CCSDT-CCSD(T) (T3-(T)), CCSDT(Q)-CCSDT ((Q)), and CCSDTQ-CCSDT(Q) (T4-(Q)) contributions from cc-pV{5,6}Z extrapolations for a diverse set of 16 first-and second-row systems. We use these basis-set limit results to fit extrapolation exponents in conjunction with the cc-pV{D,T}Z, cc-pV{T,Q}Z, and cc-pV{Q,5}Z basis set pairs. The optimal extrapolation exponents result in noticeable improvements in performance (relative to  = 3.0) in conjunction with the cc-pV{T,Q}Z basis set pair, however, smaller improvements are obtained for the other basis sets.These results confirm that the basis sets and basis set extrapolations used for obtaining post-CCSD(T) components in composite thermochemical theories such as Weizmann-4 and HEAT are sufficiently close to the CBS limit for attaining sub-kJ-per-mole accuracy. The fitted extrapolation exponents demonstrate that the T3-(T) correlation component converges more slowly to the CBS limit than the (Q) and T4 terms. A systematic investigation of the effect of

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On the performance of various hierarchized bases in extrapolating the correlation energy to the complete basis set limit

Cited by 29 publications

References 42 publications

Straightening the Hierarchical Staircase for Basis Set Extrapolations: A Low-Cost Approach to High-Accuracy Computational Chemistry

Straightening the Hierarchical Staircase for Basis Set Extrapolations: A Low-Cost Approach to High-Accuracy Computational Chemistry

On the Interplay between Charge‐Shift Bonding and Halogen Bonding

Effective basis set extrapolations for CCSDT, CCSDT(Q), and CCSDTQ correlation energies

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