Communication: The performance of non-iterative coupled cluster quadruples models

Eriksen, Janus J.; Matthews, Devin A.; Jørgensen, Poul; Gauß, Jürgen

doi:10.1063/1.4927247

Cited by 22 publications

(26 citation statements)

References 38 publications

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“…244 For CCSDT and other iterative triples methods, this technique essentially "freezes" the higher-order cluster amplitudes and their contributions to the singles and doubles while a number of (modified) CCSD Table IV. 135 From these results, we can see that CCSDT(Q-3) can reduce errors by approximately one order of magnitude compared to CCSDT(Q) at the expense of one M 10 step.…”

Section: Please Cite This Article As Doi:101063/50004837mentioning

confidence: 79%

“…the Λ equations) and potentially to EOM-CC as well.The availability of a high-performance yet easily extensible platform for higher-order coupled cluster has also allowed us to rapidly implement new coupled cluster-based methods. Perhaps the best example of this is the recent development of bivariational coupled cluster perturbation theory methods CCSD(T-n), CCSD(TQ-n), and CCSDT(Q-n),107,135 for which we have implemented up to n = 5, 4, and 6, respectively. These methods, with the exception of the lowest-order correction, scale formally the same as the full method (CCSDT or CCSDTQ), but, by recovering essentially all of the higher-order correlation energy in only a small number of high-scaling steps, a steep reduction in computational cost can be achieved.…”

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confidence: 99%

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Coupled-cluster techniques for computational chemistry: The CFOUR program package

Matthews

Cheng

Harding

et al. 2020

The Journal of Chemical Physics

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An up-to-date overview of the CFOUR program system is given. After providing a brief outline of the evolution of the program since its inception in 1989, a comprehensive presentation is given of its well-known capabilities for high-level coupled-cluster theory and its application to molecular properties. Subsequent to this generally well-known background information, much of the remaining content focuses on lesser-known capabilities of CFOUR, most of which have become available to the public only recently or will become available in the near future. Each of these new features is illustrated by a representative example, with additional discussion targeted to educating users as to classes of applications that are now enabled by these capabilities. Finally, some speculation about future directions is given, and the mode of distribution and support for CFOUR are outlined in the appendix.

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Section: Please Cite This Article As Doi:101063/50004837mentioning

confidence: 79%

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confidence: 99%

Coupled-cluster techniques for computational chemistry: The CFOUR program package

Matthews

Cheng

Harding

et al. 2020

The Journal of Chemical Physics

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550

396

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“…As examples of the second type, the CCSD(T-n), CCSD(TQ-n), and CCSDT(Qn) series have all recently been proposed, [31][32][33][34] forming order expansions that converge from either the CCSD or CCSDT energies onto the CCSDT or CCSDTQ energies, subject to the same partitioning of the electronic Hamiltonian as that used in MP theory, i.e.,Ĥ =f +Φ. …”

Section: Introductionmentioning

confidence: 99%

Convergence of coupled cluster perturbation theory

Eriksen

Kristensen

Matthews

et al. 2016

The Journal of Chemical Physics

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The convergence of a recently proposed coupled cluster (CC) family of perturbation series [Eriksen et al., J. Chem. Phys. 140, 064108 (2014)], in which the energetic difference between two CC models-a low-level parent and a high-level target model-is expanded in orders of the Møller-Plesset (MP) fluctuation potential, is investigated for four prototypical closed-shell systems (Ne, singlet CH 2 , distorted HF, and F − ) in standard and augmented basis sets. In these investigations, energy corrections of the various series have been calculated to high orders and their convergence radii determined by probing for possible front-and back-door intruder states, the existence of which would make the series divergent. In summary, we conclude how it is primarily the choice of target state, and not the choice of parent state, which ultimately governs the convergence behavior of a given series. For example, restricting the target state to, say, triple or quadruple excitations might remove intruders present in series that target the full * To whom correspondence should be addressed † Johannes Gutenberg-Universität Mainz ‡ Aarhus University ¶ The University of Texas at Austin 1 arXiv:1609.03945v2 [physics.chem-ph] 17 Jan 2017 configuration interaction (FCI) limit, such as the standard MP series. Furthermore, we find that whereas a CC perturbation series might converge within standard correlation consistent basis sets, it may start to diverge whenever these become augmented by diffuse functions, similar to the MP case. However, unlike for the MP case, such potential divergences are not found to invalidate the practical use of the low-order corrections of the CC perturbation series.2

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“…An economical way to take them into account is offered by non-iterative schemes such as CCSDT[Q] [126][127][128] or CCSDT(Q). [129][130][131] In particular, the latter method was found to systematically improve the quality of the results, 132 in comparison to both CCSD(T) and CCSDT, at a reasonable computational cost. Nowadays the CCSDT(Q) method is often regarded as the "platinum standard" of the electronic structure theory, 133 by analogy to the "gold standard" CCSD(T), and is a member of composite schemes routinely applied, e.g., in ab initio computational thermochemistry.…”

Section: Discussionmentioning

confidence: 95%

Near-exact CCSDT energetics from rank-reduced formalism supplemented by non-iterative corrections

Lesiuk

2021

Preprint

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We introduce a non-iterative energy correction, added on top of the rank-reduced coupled-cluster method with single, double, and triple substitutions, that accounts for excitations excluded from the parent triple excitation subspace. The formula for the correction is derived by employing the coupled-cluster Lagrangian formalism with an additional assumption that the parent excitation subspace is closed under the action of the Fock operator. Owning to the rank-reduced form of the triple excitation amplitudes tensor, the computational cost of evaluating the correction scales as N 7 with the system size, N . The accuracy and computational efficiency of the proposed method is assessed both for total and relative correlation energies. We show that the non-iterative correction can fulfill two separate roles. If an accuracy level of a fraction of kJ/mol is sufficient for a given system the correction significantly reduces the dimension of the parent triple excitation subspace needed in the iterative part of the calculations.Simultaneously, it enables to reproduce the exact CCSDT results to an accuracy level below 0.1 kJ/mol with a larger, yet still reasonable, dimension of the parent excitation

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Communication: The performance of non-iterative coupled cluster quadruples models

Abstract: Articles you may be interested inGaussian basis sets for use in correlated molecular calculations. I. The atoms boron through neon and

Cited by 22 publications

References 38 publications

Coupled-cluster techniques for computational chemistry: The CFOUR program package

Coupled-cluster techniques for computational chemistry: The CFOUR program package

Convergence of coupled cluster perturbation theory

Near-exact CCSDT energetics from rank-reduced formalism supplemented by non-iterative corrections

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