State-of-the-art local correlation methods enable affordable gold standard quantum chemistry for up to hundreds of atoms

Nagy, Péter R.

doi:10.1039/d4sc04755a

Chem. Sci.

2024

DOI: 10.1039/d4sc04755a

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State-of-the-art local correlation methods enable affordable gold standard quantum chemistry for up to hundreds of atoms

Péter R. Nagy

Abstract: We review the current capabilities of local electron correlation methods up to the gold standard CCSD(T) level, which are now capable of routinely reaching large systems of practical interest in p- and d-block, as well as surface and biochemistry.

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Cited by 4 publications

References 284 publications

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Advancing Non-Atom-Centered Basis Methods for More Accurate Interaction Energies: Benchmarks and Large-Scale Applications

Lőrincz,

Nagy

2024

J. Phys. Chem. A

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Recent advances in local electron correlation approaches have enabled the relatively routine access to CCSD(T) [that is, coupled cluster (CC) with single, double, and perturbative triple excitations] computations for molecules of a hundred or more atoms. Here, approaching their complete basis set (CBS) limit becomes more challenging due to extensive basis set superposition errors, often necessitating the use of large atomic orbital (AO) basis sets with diffuse functions. Here, we study a potential remedy in the form of non-atom-centered or floating orbitals (FOs). FOs are still rarely employed even for small molecules due to the practical complication of defining their position, number, exponents, etc. The most frequently used FO method thus simply places a single FO center with a large number of FOs toward the middle of noncovalent dimers; however, a single FO center for larger complexes can soon become insufficient. A recent alternative uses a grid of FO centers around the monomers with a single s function per center, which is currently applicable only for H, C, N, and O atoms. Here, we build on the above advantages and mitigate some drawbacks of previous FO approaches by using a layer of FO centers and 4−9 FOs/center for each monomer. Thus, a double layer of FOs is placed between the interacting subsystems. When extending the double-ζ AO basis with this double layer of FOs, the quality of conventional augmented double-ζ or conventional triple-ζ AO bases can be reached or surpassed with less orbitals, leading to few tenths of a kcal/mol basis set errors for medium-sized dimers. This good performance extends to larger molecules (shown here up to 72 atoms), as efficient local natural orbital (LNO) CCSD(T) computations with only double-ζ AO and 4 FOs/center FO bases match our LNO−CCSD(T)/CBS reference within ca. 0.1 kcal/mol. These developments introduce FO methods to the accurate modeling of large molecular complexes without limitations to atom types by further accelerating efficient correlation calculations, like LNO−CCSD(T).

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Advancing Non-Atom-Centered Basis Methods for More Accurate Interaction Energies: Benchmarks and Large-Scale Applications

Lőrincz,

Nagy

2024

J. Phys. Chem. A

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The “chemical tug-of-war” in carborane clusters: distinct tuning on different sides of the cluster

Buzsáki,

Gál,

Szathmári

et al. 2025

Inorg. Chem. Front.

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Canonical coupled cluster binding benchmark for nanoscale noncovalent complexes at the hundred-atom scale

Lao

2024

The Journal of Chemical Physics

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In this study, we introduce two datasets for nanoscale noncovalent binding, featuring complexes at the hundred-atom scale, benchmarked using coupled cluster with single, double, and perturbative triple [CCSD(T)] excitations extrapolated to the complete basis set (CBS) limit. The first dataset, L14, comprises 14 complexes with canonical CCSD(T)/CBS benchmarks, extending the applicability of CCSD(T)/CBS binding benchmarks to systems as large as 113 atoms. The second dataset, vL11, consists of 11 even larger complexes, evaluated using the local CCSD(T)/CBS method with stringent thresholds, covering systems up to 174 atoms. We compare binding energies obtained from local CCSD(T) and fixed-node diffusion Monte Carlo (FN-DMC), which have previously shown discrepancies exceeding the chemical accuracy threshold of 1 kcal/mol in large complexes, with the new canonical CCSD(T)/CBS results. While local CCSD(T)/CBS agrees with canonical CCSD(T)/CBS within binding uncertainties, FN-DMC consistently underestimates binding energies in π–π complexes by over 1 kcal/mol. Potential sources of error in canonical CCSD(T)/CBS are discussed, and we argue that the observed discrepancies are unlikely to originate from CCSD(T) itself. Instead, the fixed-node approximation in FN-DMC warrants further investigation to elucidate these binding discrepancies. Using these datasets as reference, we evaluate the performance of various electronic structure methods, semi-empirical approaches, and machine learning potentials for nanoscale complexes. Based on computational accuracy and stability across system sizes, we recommend MP2+aiD(CCD), PBE0+D4, and ωB97X-3c as reliable methods for investigating noncovalent interactions in nanoscale complexes, maintaining their promising performance observed in smaller systems.

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State-of-the-art local correlation methods enable affordable gold standard quantum chemistry for up to hundreds of atoms

Abstract: We review the current capabilities of local electron correlation methods up to the gold standard CCSD(T) level, which are now capable of routinely reaching large systems of practical interest in p- and d-block, as well as surface and biochemistry.

Cited by 4 publications

References 284 publications

Advancing Non-Atom-Centered Basis Methods for More Accurate Interaction Energies: Benchmarks and Large-Scale Applications

Advancing Non-Atom-Centered Basis Methods for More Accurate Interaction Energies: Benchmarks and Large-Scale Applications

The “chemical tug-of-war” in carborane clusters: distinct tuning on different sides of the cluster

Canonical coupled cluster binding benchmark for nanoscale noncovalent complexes at the hundred-atom scale

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