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Related papers: Factorized Quadruples and a Predictor of Higher-Le…

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A major difficulty in quantum simulation is the adequate treatment of a large collection of entangled particles, synonymous with electron correlation in electronic structure theory, with coupled cluster (CC) theory being the leading…

Chemical Physics · Physics 2024-06-06 Zachary W. Windom , Daniel Claudino , Rodney J. Bartlett

Obtaining sub-chemical accuracy (1 kJ mol${}^{-1}$) for reaction energies of medium-sized gas-phase molecules is a longstanding challenge in the field of thermochemical modeling. The perturbative triples correction to CCSD, CCSD(T),…

Chemical Physics · Physics 2025-03-26 Tingting Zhao , James H. Thorpe , Devin A. Matthews

We propose a non-iterative, post hoc correction to the unitary coupled cluster theory with single, double, and triple excitations (UCCSDT) ansatz, which considers the leading-order effects of neglected quadruple excitations. We present two…

Chemical Physics · Physics 2025-08-14 Zachary W. Windom , Luke Bertels , Daniel Claudino , Rodney J. Bartlett

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…

Chemical Physics · Physics 2022-07-01 Dylan Fowler , Kurt R. Brorsen

We consider the rank-reduced coupled-cluster theory with single and double excitations (RR-CCSD) introduced recently [Parrish \emph{et al.}, J. Chem. Phys. {\bf 150}, 164118 (2019)]. The main feature of this method is the decomposed form of…

Chemical Physics · Physics 2022-02-21 Michał Lesiuk

The accuracy at which total energies of open-shell atoms and organic radicals may be calculated is assessed for selected coupled cluster perturbative triples expansions, all of which augment the coupled cluster singles and doubles (CCSD)…

Chemical Physics · Physics 2016-05-17 Janus Juul Eriksen , Devin A. Matthews , Poul Jørgensen , Jürgen Gauss

In this work, we introduce a correction to the unitary coupled cluster method with single and double excitations (UCCSD) that incorporates the effects of missing triple excitations through a treatment that is correct through fifth-order in…

Chemical Physics · Physics 2025-09-08 Zachary W. Windom , Daniel Claudino

Basis set convergence of correlation effects on molecular atomization energies beyond the CCSD (coupled cluster with singles and doubles) approximation has been studied near the one-particle basis set limit. Quasiperturbative connected…

Chemical Physics · Physics 2008-08-17 Amir Karton , Peter R. Taylor , Jan M. L. Martin

In an attempt to improve on our earlier W3 theory [J. Chem. Phys. {\bf 120}, 4129 (2004)] we consider such refinements as more accurate estimates for the contribution of connected quadruple excitations ($\hat{T}_4$), inclusion of connected…

Chemical Physics · Physics 2007-05-23 Amir Karton , Elena Rabinovich , Jan M. L. Martin , Branko Ruscic

In this article we study the effects of higher body excitations in the relativistic CC calculations for atoms and ions with one valence electron using Fock-space CCSD, CCSD(T) and its unitary variants. The present study demonstrates that…

Atomic Physics · Physics 2009-11-13 Chiranjib Sur , Rajat K Chaudhuri

In order to explore the effects of high levels of electron correlation on the real-time coupled cluster formalism and algorithmic behavior, we introduce a time-dependent implementation of the CC3 singles, doubles and approximate triples…

Chemical Physics · Physics 2025-01-23 Zhe Wang , Håkon Emil Kristiansen , Thomas Bondo Pedersen , T. Daniel Crawford

We present a perturbative triples correction to the relativistic quadratic unitary coupled cluster singles and doubles (qUCCSD) method, denoted as qUCCSD[T]. The method builds upon the Hermitian structure of the unitary ansatz and employs a…

Chemical Physics · Physics 2025-10-08 Kamal Majee , Ján Šimunek , Jozef Noga , Achintya Kumar Dutta

We extend our assessment of the potential of perturbative coupled cluster (CC) expansions for a test set of open-shell atoms and organic radicals to the description of quadruple excitations. Namely, the second- through sixth-order models of…

Chemical Physics · Physics 2016-05-17 Janus J. Eriksen , Devin A. Matthews , Poul Jørgensen , Jürgen Gauss

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…

Chemical Physics · Physics 2023-05-29 Mohammad Haidar , Marko J. Rančić , Yvon Maday , Jean-Philip Piquemal

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…

Chemical Physics · Physics 2025-05-14 S. Lambie , C. Rickert , D. Usvyat , A. Alavi , D. Kats

Fourth-order many-body corrections to matrix elements for atoms with one valence electron are derived. The obtained diagrams are classified using coupled-cluster-inspired separation into contributions from n-particle excitations from the…

Atomic Physics · Physics 2009-11-07 Andrei Derevianko , Erik D. Emmons

We are proposing a new computational thermochemistry protocol denoted W3 theory, as a successor to W1 and W2 theory proposed earlier [Martin and De Oliveira, J. Chem. Phys. 111, 1843 (1999)]. The new method is both more accurate overall…

Chemical Physics · Physics 2007-05-23 A. Daniel Boese , Mikhal Oren , Onur Atasoylu , Jan M. L. Martin , Mihaly Kallay , Juergen Gauss

To follow up on the unexpectedly-good performance of several coupled-cluster models with approximate inclusion of 3-body clusters [J. Chem. Phys. 151, 064102 (2019)] we performed a more complete assessment of the 3CC method [J. Chem. Phys.…

Chemical Physics · Physics 2025-10-13 Nakul Teke , Ajay Melekamburath , Bimal Gaudel , Edward F. Valeev

We present the working equations for a reduced-scaling method of evaluating the perturbative triples (T) energy in coupled-cluster theory, through the tensor hypercontraction (THC) of the triples amplitudes ($t_{ijk}^{abc}$). Through our…

Chemical Physics · Physics 2024-06-12 Andy Jiang , Justin M. Turney , Henry F. Schaefer

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…

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