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Wavefunctions restricted to electron pair states are promising models for strongly-correlated systems. Specifically, the pair Coupled Cluster Doubles (pCCD) ansatz allows us to accurately describe bond dissociation processes and…

Strongly Correlated Electrons · Physics 2019-05-01 Katharina Boguslawski

We present a basis set correction scheme for the coupled-cluster singles and doubles (CCSD) method. The scheme is based on employing frozen natural orbitals (FNOs) and diagrammatically decomposed contributions to the electronic correlation…

Materials Science · Physics 2021-06-18 Andreas Irmler , Alejandro Gallo , Andreas Grüneis

Electron correlation effects are essential for an accurate ab initio description of molecules. A quantitative a priori knowledge of the single- or multi-reference nature of electronic structures as well as of the dominant contributions to…

Quantum Physics · Physics 2012-12-18 Katharina Boguslawski , Paweł Tecmer , Örs Legeza , Markus Reiher

Slater determinants underpin most electronic structure methods, but orbital-based approaches often struggle to describe strong correlation efficiently. Geminal-based theories, by contrast, naturally capture static correlation in…

We report the formulation of a new, cost-effective approximation method in the time-dependent optimized coupled-cluster (TD-OCC) framework [T. Sato et al., J. Chem. Phys. 148, 051101 (2018)] for first-principles simulations of multielectron…

Chemical Physics · Physics 2022-08-11 Himadri Pathak , Takeshi Sato , Kenichi L. Ishikawa

We present a novel approach to spin-adapted coupled cluster theory. This approach is based on the entanglement of an open-shell molecule with electrons in a non-interacting bath; together they form a closed-shell state. For the total…

Chemical Physics · Physics 2023-05-22 Sarai Dery Folkestad , Bendik Støa Sannes , Henrik Koch

Electrodynamical coupled cluster (CC) methodologies have been formulated employing standard QED Hamiltonian that is written in Coulomb gauge while using the DF and the MCDF pictures of the matter field for closed-shell and open-shell cases…

Quantum Physics · Physics 2024-01-15 Sambhu N. Datta

The chemical bond is an important local concept to understand chemical compounds and processes. Unfortunately, like most local concepts, the chemical bond and the bond order do not correspond to any physical observable and thus cannot be…

Strongly Correlated Electrons · Physics 2017-09-13 Matthieu Mottet , Pawel Tecmer , Katharina Boguslawski , Ors Legeza , Markus Reiher

We investigate the use of orbital-optimized references in conjunction with single-reference coupled-cluster theory with single and double substitutions (CCSD) for the study of core excitations and ionizations of 18 small organic molecules,…

A unitary coupled-cluster (UCC) form for the wavefunction in the variational quantum eigensolver has been suggested as a systematic way to go beyond the mean-field approximation and include electron correlation in solving quantum chemistry…

Quantum Physics · Physics 2018-09-12 Ilya G. Ryabinkin , Tzu-Ching Yen , Scott N. Genin , Artur F. Izmaylov

The previously proposed ansatz for density cumulant theory that combines orbital-optimization and a parameterization of the 2-electron reduced density matrix cumulant in terms of unitary coupled cluster amplitudes (OUDCT) is carefully…

Chemical Physics · Physics 2020-12-23 Jonathon P. Misiewicz , Justin M. Turney , Henry F. Schaefer , Alexander Yu. Sokolov

Physics of high-$T_c$ superconducting cuprates is obscured by the effect of strong electronic correlations. One way to overcome the problem is to seek for an exact solution at least within the small cluster and expand it to the whole…

Strongly Correlated Electrons · Physics 2023-07-19 V. I. Kuz'min , S. V. Nikolaev , M. M. Korshunov , S. G. Ovchinnikov

A unitary coupled-cluster (UCC)-based self-consistent electron propagator theory (EPT) is proposed for the description of electron-detached and electron-attached states. Two practical schemes, termed IP/EA-UCC3 and IP/EA-qUCCSD, are…

Chemical Physics · Physics 2026-03-03 Yu Zhang , Junzi Liu

Density functional theory (DFT) is the most widely used method for calculating molecular properties; however, its accuracy is often insufficient for quantitative predictions. Coupled-cluster (CC) theory is the most successful method for…

We calculate correlation functions of exactly-solvable one-dimensional flat-band models by utilizing the "molecular-orbital" representation. The models considered in this paper have a gapped ground state with flat-band being fully occupied,…

Strongly Correlated Electrons · Physics 2022-03-23 Tomonari Mizoguchi , Yoshihito Kuno , Yasuhiro Hatsugai

We reveal limitations of several standard coupled-cluster (CC) methods with perturbation-theorybased noniterative or approximate iterative treatments of triple excitations when applied to thedetermination of highly accurate potential energy…

Chemical Physics · Physics 2021-10-04 Jan Schnabel , Lan Cheng , Andreas Köhn

We introduce a unitary coupled-cluster (UCC) ansatz termed $k$-UpCCGSD that is based on a family of sparse generalized doubles (D) operators which provides an affordable and systematically improvable unitary coupled-cluster wavefunction…

Quantum Physics · Physics 2019-01-07 Joonho Lee , William J. Huggins , Martin Head-Gordon , K. Birgitta Whaley

The issue of orbital relaxation in computational core-hole spectroscopy, specifically x-ray absorption, has been a major problem for methods such as equation-of-motion coupled cluster with singles and doubles (EOM-CCSD). The…

Chemical Physics · Physics 2025-03-26 Megan Simons , Devin A. Matthews

Accurately describing strong electron correlation in complex systems remains a prominent challenge in computational chemistry as near-term quantum algorithms treating total correlation often require prohibitively deep circuits. Here we…

Computational Engineering, Finance, and Science · Computer Science 2026-04-21 Zhanou Liu , Yuhao Chen , Yingjin Ma , Xiao He , Yuxin Deng

We present an efficient approach to the electron correlation problem that is well-suited for strongly interacting many-body systems, but requires only mean-field-like computational cost. %which is based on orbital optimization of electron…

Strongly Correlated Electrons · Physics 2014-08-05 Katharina Boguslawski , Paweł Tecmer , Paul W. Ayers , Patrick Bultinck , Stijn De Baerdemacker , Dimitri Van Neck