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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

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

Simulating molecules using the Variational Quantum Eigensolver method is one of the promising applications for NISQ-era quantum computers. Designing an efficient ansatz to represent the electronic wave function is crucial in such…

Chemical Physics · Physics 2022-05-09 Dmitry A. Fedorov , Yuri Alexeev , Stephen K. Gray , Matthew Otten

In truncated coupled-cluster (CC) theories, non-variational and/or generally complex ground-state energies can occur. This is due to the non-Hermitian nature of the similarity transformed Hamiltonian matrix in combination with CC…

Chemical Physics · Physics 2023-09-22 Tanner Culpitt , Erik I. Tellgren , Fabijan Pavosevic

An implementation of the coupled-cluster single- and double excitations (CCSD) method on two-dimensional quantum dots is presented. Advantages and limitations are studied through comparison with other high accuracy approaches for two to…

Mesoscale and Nanoscale Physics · Physics 2013-05-30 Erik Waltersson , Eva Lindroth

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

We present a four-component relativistic unitary coupled cluster method for molecules. We have used commutator-based non-perturbative approximation using the ''Bernoulli expansion'' to derive an approximation to the relativistic unitary…

Chemical Physics · Physics 2024-03-06 Kamal Majee , Tamoghna Mukhopadhyay , Malaya K. Nayak , Achintya Kumar Dutta

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 recent quantum information boom has effected a resurgence of interest in unitary coupled cluster (UCC) theory. Our group's interest in local energy landscapes of unitary ans\"atze prompted us to investigate the classical approach of…

Chemical Physics · Physics 2022-11-01 Harper R. Grimsley , Nicholas J. Mayhall

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 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…

We propose a relativistic unitary coupled cluster (UCC) expectation value approach for computing first-order properties of heavy-element systems. Both perturbative (UCC3) and non-perturbative (qUCC) commutator-based formulations are applied…

Chemical Physics · Physics 2026-02-03 Kamal Majee , Somesh Chamoli , Malaya K. Nayak , Achintya Kumar Dutta

Unitary coupled cluster (UCC) theory offers a promising Hermitian alternative to conventional coupled cluster (CC) theory, but its practical implementation is hindered by the non-truncating nature of the Baker-Campbell-Hausdorff (BCH)…

Chemical Physics · Physics 2025-05-05 Justin T. Phillips , Lauren N. Koulias , Stephen H. Yuwono , A. Eugene DePrince

Coupled cluster methods based exclusively on double excitations are comparatively "cheap" and interesting model chemistries, as they are typically able to capture the bulk of the dynamical electron correlation effects. The trade-off in such…

Quantum Physics · Physics 2024-06-14 Zachary W. Windom , Daniel Claudino , Rodney J. Bartlett

Unitary Coupled Cluster (UCC) theory is a promising variational method for electronic structure calculations, especially for strongly correlated systems and quantum computers. However, its practical application is limited by the steep…

Chemical Physics · Physics 2026-02-05 Prateek Vaish , Brenda Rubenstein

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

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…

Chemical Physics · Physics 2023-11-27 Harrison Tuckman , Eric Neuscamman

In single-reference coupled-cluster (CC) methods, one has to solve a set of non-linear polynomial equations in order to determine the so-called amplitudes which are then used to compute the energy and other properties. Although it is of…

Chemical Physics · Physics 2021-09-10 Antoine Marie , Fábris Kossoski , Pierre-François Loos

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

We derive the coupled-cluster doubles (CCD) amplitude equations by introduction of the particle-hole-time decoupled electronic self-energy. The resulting analysis leads to an expression for the ground state correlation energy that is…

Strongly Correlated Electrons · Physics 2025-09-09 Christopher J. N. Coveney
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