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The fundamental non-Hermitian nature of the forms of coupled-cluster (CC) theory widely used in quantum chemistry has usually been viewed as a negative, but the present letter shows how this can be used to advantage. Specifically, the…

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…

Chemical Physics · Physics 2025-12-12 Ilias Magoulas , Jun Shen , Piotr Piecuch

Coupled cluster theory is the method of choice for weakly correlated systems. But in the strongly correlated regime, it faces a symmetry dilemma, where it either completely fails to describe the system, or has to artificially break certain…

Chemical Physics · Physics 2020-05-14 Yiheng Qiu , Thomas M. Henderson , Jinmo Zhao , Gustavo E. Scuseria

There have been assertions in the literature that the variational and unitary forms of coupled cluster theory lead to the same energy functional. Numerical evidence from previous authors was inconsistent with this claim, yet the small…

Strongly Correlated Electrons · Physics 2020-05-14 Gaurav Harsha , Toru Shiozaki , Gustavo E. Scuseria

Methods which aim at universal applicability must be able to describe both weak and strong electronic correlation with equal facility. Such methods are in short supply. The combination of symmetry projection for strong correlation and…

Chemical Physics · Physics 2020-05-14 Yiheng Qiu , Thomas M. Henderson , Jinmo Zhao , Gustavo E. Scuseria

Computationally efficient and accurate quantum mechanical approximations to solve the many-electron Schr\"odinger equation are at the heart of computational materials science. In that respect the coupled cluster hierarchy of methods plays a…

Materials Science · Physics 2022-01-11 Tina N. Mihm , Tobias Schäfer , Sai Kumar Ramadugu , Andreas Grüneis , James J. Shepherd

Inspired by our earlier semi-stochastic work aimed at converging high-level coupled-cluster (CC) energetics [J. E. Deustua, J. Shen, and P. Piecuch, Phys. Rev. Lett. 119, 223003 (2017); J. Chem. Phys. 154, 124103 (2021)], we propose a novel…

Chemical Physics · Physics 2022-10-06 Karthik Gururangan , J. Emiliano Deustua , Jun Shen , Piotr Piecuch

An implementation of coupled-cluster (CC) theory to treat atoms and molecules in finite magnetic fields is presented. The main challenges stem from the magnetic-field dependence in the Hamiltonian, or, more precisely, the appearance of the…

Chemical Physics · Physics 2015-09-02 Stella Stopkowicz , Jürgen Gauss , Kai K. Lange , Erik I. Tellgren , Trygve Helgaker

Coupled cluster theory is a vital cornerstone of electronic structure theory and is being applied to ever-larger systems. Stochastic approaches to quantum chemistry have grown in importance and offer compelling advantages over traditional…

We investigate the accuracy of a number of wavefunction based methods at the heart of quantum chemistry for metallic systems. Using Hartree-Fock as a reference, perturbative (M{\o}ller-Plesset, MP) and coupled cluster (CC) theories are used…

Chemical Physics · Physics 2013-10-24 James J. Shepherd , Andreas Grüneis

We consider the sampling of the coupled cluster expansion within stochastic coupled cluster theory. Observing the limitations of previous approaches due to the inherently non-linear behaviour of a coupled cluster wavefunction representation…

Chemical Physics · Physics 2018-08-14 Charles J. C. Scott , Alex J. W. Thom

In strongly coupled field theories, perturbation theory cannot be employed to study the low-energy spectrum. Thus, non-perturbative techniques are required. We employ the variational method, a rigorous, non-perturbative approach which…

High Energy Physics - Lattice · Physics 2024-09-27 M. Rovira , A. Parreño , R. J. Perry

The cluster variation method (CVM) is a hierarchy of approximate variational techniques for discrete (Ising--like) models in equilibrium statistical mechanics, improving on the mean--field approximation and the Bethe--Peierls approximation,…

Statistical Mechanics · Physics 2007-07-16 Alessandro Pelizzola

Recently developed pair coupled cluster doubles (pCCD) theory successfully reproduces doubly occupied configuration interaction (DOCI) with mean field cost. However, the projective nature of pCCD makes the method non-variational and thus…

Chemical Physics · Physics 2016-08-19 Luning Zhao , Eric Neuscamman

We discuss diagrammatic modifications to the coupled cluster doubles (CCD) equations, wherein different groups of terms out of rings, ladders, crossed-rings and mosaics can be removed to form approximations to the coupled cluster method, of…

Chemical Physics · Physics 2014-05-06 James J. Shepherd , Thomas. M. Henderson , Gustavo E. Scuseria

Precision tests of QCD perturbation theory are not readily available from experimental data. The main reasons are systematic uncertainties due to the confinement of quarks and gluons, as well as kinematical constraints which limit the…

High Energy Physics - Lattice · Physics 2017-04-05 Stefan Sint

Introducing an active space approximation is inevitable for the quantum computations of chemical systems. However, this approximation ignores the electron correlations related to non-active orbitals. Here, we propose a computational method…

Quantum Physics · Physics 2024-06-06 Luca Erhart , Yuichiro Yoshida , Viktor Khinevich , Wataru Mizukami

Quantum periodic cluster methods for strongly correlated electron systems are reformulated and developed. The reformulation and development are based on a canonical transformation which periodizes the fermions in the cluster space. The…

Strongly Correlated Electrons · Physics 2007-05-23 Tran Minh-Tien

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

The convergence of a recently proposed coupled cluster (CC) family of perturbation series [Eriksen, J. J. et al., J. Chem. Phys. 140, 064108 (2014)], in which the energetic difference between two CC models - a low-level parent and a…

Chemical Physics · Physics 2017-01-18 Janus Juul Eriksen , Kasper Kristensen , Devin A. Matthews , Poul Jørgensen , Jeppe Olsen