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While limited coupled cluster theory is \textit{formally} nonvariational, it is not broadly appreciated whether this is a major issue \textit{in practice}. We carried out a detailed comparison with \textit{de facto} full CI energies for a…

化学物理 · 物理学 2024-10-03 Jan M. L. Martin , Emmanouil Semidalas

Recent disagreement between state-of-the-art quantum chemical methods, coupled cluster with single, double and perturbative triples excitations and fixed-node diffusion Monte Carlo, calls for systematic examination of possible sources of…

化学物理 · 物理学 2025-05-14 S. Lambie , C. Rickert , D. Usvyat , A. Alavi , D. Kats

Coupled-cluster theory with single, double, and perturbative triple excitations (CCSD(T)) -- often considered the "gold standard" of main-group quantum chemistry -- is inapplicable to three-dimensional metals due to an infrared divergence,…

材料科学 · 物理学 2023-03-21 Verena A. Neufeld , Timothy C. Berkelbach

Understanding the process of molecular photoexcitation is crucial in various fields, including drug development, materials science, photovoltaics, and more. The electronic vertical excitation energy is a critical property, for example in…

化学物理 · 物理学 2025-03-26 Tingting Zhao , Devin A. Matthews

A new method that accurately describes strongly correlated states and captures dynamical correlation is presented. It is derived as a modification of coupled-cluster theory with single and double excitations (CCSD) through consideration of…

化学物理 · 物理学 2013-07-15 Daniel Kats , Frederick R. Manby

A novel approach to rapidly converging high-level coupled-cluster (CC) energetics in an automated fashion is proposed. The key idea is an adaptive selection of the excitation manifolds defining higher-than-two-body components of the cluster…

化学物理 · 物理学 2023-08-25 Karthik Gururangan , Piotr Piecuch

The coupled cluster method is considered a gold standard in quantum chemistry, reliably giving energies that are exact within chemical accuracy (1.6 mHartree). However, even in the CCSD approximation, where the cluster operator is truncated…

化学物理 · 物理学 2023-03-10 Simon Elias Schrader , Simen Kvaal

In the molecular quantum chemistry community, coupled-cluster (CC) methods are well-recognized for their systematic convergence and reliability. The extension of the theory to extended systems has been comparably recent, so that…

化学物理 · 物理学 2024-10-31 Andreas Grüneis , Evgeny Moerman , Matthias Scheffler , Tonghao Shen , Igor Ying Zhang

An accurate determination of singlet-triplet gaps in biradicals, including cyclobutadiene in the automerization barrier region where one has to balance the substantial nondynamical many-electron correlation effects characterizing the…

化学物理 · 物理学 2025-12-23 Swati S. Priyadarsini , Karthik Gururangan , Jun Shen , Piotr Piecuch

When the number of strongly correlated electrons becomes larger, the single-reference coupled-cluster (CC) CCSD, CCSDT, etc. hierarchy displays an erratic behavior, while traditional multi-reference approaches may no longer be applicable…

化学物理 · 物理学 2025-12-12 Ilias Magoulas , Jun Shen , Piotr Piecuch

We present an excited-state-specific coupled-cluster approach in which both the molecular orbitals and cluster amplitudes are optimized for an individual excited state. The theory is formulated via a pseudoprojection of the traditional…

化学物理 · 物理学 2023-11-27 Harrison Tuckman , Eric Neuscamman

The (T) and [T] perturbative corrections are derived for multicomponent coupled-cluster theory with single and double excitations (CCSD). Benchmarking shows that multicomponent CCSD methods that include the perturbative corrections are more…

化学物理 · 物理学 2022-07-01 Dylan Fowler , Kurt R. Brorsen

The Trotterized Unitary Coupled Cluster Single and Double (UCCSD) ansatz has recently attracted interest due to its use in Variation Quantum Eigensolver (VQE) molecular simulations on quantum computers. However, when the size of molecules…

化学物理 · 物理学 2023-05-29 Mohammad Haidar , Marko J. Rančić , Yvon Maday , Jean-Philip Piquemal

We report a complete implementation of the coupled-cluster method with single, double, and triple excitations (CCSDT) where tensor decompositions are used to reduce its scaling and overall computational costs. For the decomposition of the…

化学物理 · 物理学 2020-02-20 Michał Lesiuk

We consider two distinct coupled cluster (CC) perturbation series that both expand the difference between the energies of the CCSD (CC with single and double excitations) and CCSDT (CC with single, double, and triple excitations) models in…

We incorporate a solver for the fragment problem with accuracy beyond coupled cluster singles and doubles (CCSD) into the previously proposed static embedding framework, MPCC. To this end, we employ a CCSDT solver for the fragment…

化学物理 · 物理学 2026-02-16 Avijit Shee , Fabian M. Faulstich , K. Birgitta Whaley , Lin Lin , Martin Head-Gordon

The method of sub-iteration, which was previously applied to the higher-order coupled cluster amplitude equations, is extended to the case of the coupled cluster $\Lambda$ equations. The sub-iteration procedure for the $\Lambda$ equations…

化学物理 · 物理学 2025-03-26 Devin A. Matthews

A number of iterative and perturbative approximations to the full equation-of-motion coupled cluster method with single, double, and triple excitations (EOM-CCSDT) are evaluated in the context of calculating the K-edge core-excitation and…

化学物理 · 物理学 2025-03-26 Devin A. Matthews

The Coupled Cluster (CC) method is used to compute the electronic correlation energy in atoms and molecules and often leads to highly accurate results. However, due to its single-reference nature, standard CC in its projected form fails to…

Coupled cluster theory is one of the most accurate electronic structure methods for predicting ground and excited state chemistry. However, the presence of numerical artifacts at electronic degeneracies, such as complex energies, has made…

化学物理 · 物理学 2024-05-16 Eirik F. Kjønstad , Sara Angelico , Henrik Koch
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