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The extension of the highly-optimized local natural orbital (LNO) CCSD(T) method is presented for high-spin open-shell molecules. The techniques enabling the outstanding efficiency of the closed-shell LNO-CCSD(T) variant are adopted,…

Chemical Physics · Physics 2023-11-17 P. Bernát Szabó , József Csóka , Mihály Kállay , Péter R. Nagy

Computation of heats of reaction of large molecules is now feasible using domain-based PNO-CCSD(T) theory. However, to obtain agreement within 1~kcal/mol of experiment, it is necessary to eliminate basis set incompleteness error, which…

Chemical Physics · Physics 2023-09-07 Kesha Sorathia , Damyan Frantzov , David P. Tew

We report a complete implementation of the coupled-cluster method with single, double, and triple excitations (CCSDT) where tensor decompositions are used to reduce its scaling and overall computational costs. For the decomposition of the…

Chemical Physics · Physics 2020-02-20 Michał Lesiuk

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,…

Localized orbital coupled cluster theory has recently emerged as an nonempirical alternative to DFT for large systems. Intuitively, one might expect such methods to perform less well for highly delocalized systems. In the present work, we…

Chemical Physics · Physics 2020-10-16 Nitai Sylvetsky , Ambar Banerjee , Mercedes Alonso , Jan M. L. Martin

The accurate description of nuclear quantum effects, such as zero-point energy, is important for modeling a wide range of chemical and biological processes. Within the nuclear-electronic orbital (NEO) approach, such effects are incorporated…

Chemical Physics · Physics 2022-09-07 Fabijan Pavošević , Sharon Hammes-Schiffer

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 investigate a novel approach to approximate tensor-network contraction via the exact, matrix-free decomposition of full tensor-networks. We study this method as a means to eliminate the propagation of error in the approximation of…

Chemical Physics · Physics 2025-06-23 Karl Pierce

The coupled cluster method is considered a gold standard in quantum chemistry, reliably giving energies that are exact within chemical accuracy (1.6 mHartree). However, even in the CCSD approximation, where the cluster operator is truncated…

Chemical Physics · Physics 2023-03-10 Simon Elias Schrader , Simen Kvaal

Arguably the most widely used approaches for obtaining highly accurate molecular ground-state energies are coupled cluster methods. Despite introducing two layers of approximation, a linear and a nonlinear one, coupled cluster methods…

Numerical Analysis · Mathematics 2026-05-22 Jonas Beck , Benjamin Stamm

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

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 formulate a parity-mixed coupled-cluster (PM-CC) approach for high-precision calculations of parity non-conserving amplitudes in mono-valent atoms. Compared to the conventional formalism which uses parity-proper (PP) one-electron…

Atomic Physics · Physics 2022-02-16 H. B. Tran Tan , Di Xiao , A. Derevianko

The pair coupled cluster doubles (pCCD) method (where the excitation manifold is restricted to electron pairs) has a series of interesting features. Among others, it provides ground-state energies very close to what is obtained with…

We describe the implementation details of periodic local coupled-cluster theory with single and double excitations (CCSD) and perturbative triple excitations [CCSD(T)] using local natural orbitals (LNOs) and $k$-point symmetry. We discuss…

Chemical Physics · Physics 2024-11-13 Hong-Zhou Ye , Timothy C. Berkelbach

Spectral clustering is one of the most popular clustering methods. However, the high computational cost due to the involved eigen-decomposition procedure can immediately hinder its applications in large-scale tasks. In this paper we use…

Machine Learning · Computer Science 2023-01-24 Yongyu Wang

We present domain-based local pair natural orbital M{\o}ller--Plesset second order perturbation theory (DLPNO-MP2) with Born--von K{\'a}rm{\'a}n boundary (BvK) conditions. The approach is based on well-localised Wannier functions in a LCAO…

Chemical Physics · Physics 2025-07-15 Arman Nejad , Andrew Zhu , Kesha Sorathia , David P. Tew

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

Matrix completion focuses on recovering a matrix from a small subset of its observed elements, and has already gained cumulative attention in computer vision. Many previous approaches formulate this issue as a low-rank matrix approximation…

Computer Vision and Pattern Recognition · Computer Science 2019-01-08 Shengke Xue , Wenyuan Qiu , Fan Liu , Xinyu Jin

Contributions from connected quintuple excitations in coupled cluster theory can reach the 0.5 kcal/mol range, important enough to matter in accurate computational thermochemistry, yet the very steep $\propto N^{12}$ CPU time scaling…

Chemical Physics · Physics 2026-05-22 Gregory H. Jones , Aditya Barman , Margarita Shepelenko , Jan M. L. Martin