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We provide the first rigorous study of the finite-size error in the simplest and representative coupled cluster theory, namely the coupled cluster doubles (CCD) theory, for gapped periodic systems. Assuming that the CCD equations are solved…

Numerical Analysis · Mathematics 2024-01-26 Xin Xing , Lin Lin

The study and prediction of chemical reactivity is one of the most important application areas of molecular quantum chemistry. Large-scale, fully error-tolerant quantum computers could provide exact or near-exact solutions to the underlying…

Quantum Physics · Physics 2019-09-12 Michael Kühn , Sebastian Zanker , Peter Deglmann , Michael Marthaler , Horst Weiß

Coupled cluster theory produced arguably the most widely used high-accuracy computational quantum chemistry methods. Despite the approach's overall great computational success, its mathematical understanding is so far limited to results…

Algebraic Geometry · Mathematics 2024-03-29 Fabian M. Faulstich , Mathias Oster

An iterative version of the qubit coupled cluster (QCC) method [I.G. Ryabinkin et al., J. Chem. Theory Comput. 14, 6317 (2019)] is proposed. The new method seeks to find ground electronic energies of molecules on noisy intermediate-scale…

Quantum Physics · Physics 2019-10-28 Ilya G. Ryabinkin , Robert A. Lang , Scott N. Genin , Artur F. Izmaylov

We introduce a novel algorithm that leverages stochastic sampling techniques to compute the perturbative triples correction in the coupled-cluster (CC) framework. By combining elements of randomness and determinism, our algorithm achieves a…

Chemical Physics · Physics 2024-05-29 Yann Damour , Alejandro Gallo , Anthony Scemama

Quantum computation represents a revolutionary approach for solving problems in quantum chemistry. However, due to the limited quantum resources in the current noisy intermediate-scale quantum (NISQ) devices, quantum algorithms for large…

Quantum Physics · Physics 2023-04-17 Yi Fan , Changsu Cao , Xusheng Xu , Zhenyu Li , Dingshun Lv , Man-Hong Yung

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

We introduce an unsupervised clustering algorithm to improve training efficiency and accuracy in predicting energies using molecular-orbital-based machine learning (MOB-ML). This work determines clusters via the Gaussian mixture model (GMM)…

Chemical Physics · Physics 2023-03-28 Lixue Cheng , Jiace Sun , Thomas F. Miller

We introduce affordable computational strategies for calculating orbital and pair-orbital energies in atomic and molecular systems. Our methods are based on the pair Coupled Cluster Doubles (pCCD) ansatz and its orbital-optimized variant.…

Chemical Physics · Physics 2025-02-06 Seyedehdelaram Jahani , Somayeh Ahmadkhani , Katharina Boguslawski , Paweł Tecmer

We present a near-linear scaling formulation of the explicitly-correlated coupled-cluster singles and doubles with perturbative triples method (CCSD(T)$_{\overline{\text{F12}}}$) for high-spin states of open-shell species. The approach is…

Chemical Physics · Physics 2024-07-30 Ashutosh Kumar , Frank Neese , Edward F. Valeev

Coupled cluster theory has had a momentous impact on the ab initio prediction of molecular properties, and remains a staple ingratiate in high-accuracy thermochemical model chemistries. However, these methods require inclusion of at least…

Chemical Physics · Physics 2025-03-26 James H. Thorpe , Zachary W. Windom , Rodney J. Bartlett , Devin A. Matthews

The standard and renormalized coupled cluster methods with singles, doubles, and noniterative triples and their generalizations to excited states, based on the equation of motion coupled cluster approach, are applied to the He-4 and O-16…

Nuclear Theory · Physics 2009-11-10 K. Kowalski , D. J. Dean , M. Hjorth-Jensen , T. Papenbrock , P. Piecuch

In this paper we extend the rank-reduced coupled-cluster formalism to the calculation of non-iterative energy corrections due to quadruple excitations. There are two major components of the proposed formalism. The first is an approximate…

Chemical Physics · Physics 2022-11-11 Michał Lesiuk

We give an efficient algorithm for robustly clustering of a mixture of two arbitrary Gaussians, a central open problem in the theory of computationally efficient robust estimation, assuming only that the the means of the component Gaussians…

Data Structures and Algorithms · Computer Science 2020-06-02 He Jia , Santosh Vempala

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

We recently proposed a novel approach to converging electronic energies equivalent to high-level coupled-cluster (CC) computations by combining the deterministic CC($P$;$Q$) formalism with the stochastic configuration interaction (CI) and…

Chemical Physics · Physics 2021-03-23 J. Emiliano Deustua , 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…

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

Electronic structure calculations, such as in the Hartree-Fock or Kohn-Sham density functional approach, require an initial guess for the molecular orbitals. The quality of the initial guess has a significant impact on the speed of…

Chemical Physics · Physics 2019-03-13 Susi Lehtola

The unitary cluster Jastrow (UCJ) ansatz and its variant known as local UCJ (LUCJ) are promising choices for variational quantum algorithms for chemistry due to their combination of physical motivation and hardware efficiency. The…

Quantum Physics · Physics 2025-12-01 Wan-Hsuan Lin , Fangchun Liang , Mario Motta , Haimeng Zhang , Kenneth M. Merz , Kevin J. Sung

We present an equation generator algorithm that utilizes second-quantized operators in normal order with respect to a correlated or non-correlated reference and the corresponding Wick theorem. The algorithm proposed here, written with…

Chemical Physics · Physics 2023-08-31 Raúl Quintero-Monsebaiz , Pierre-François Loos