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The tailored coupled cluster (TCC) approach is a promising ansatz that preserves the simplicity of single-reference coupled cluster theory, while incorporating a multi-reference wave function through amplitudes obtained from a preceding…

Chemical Physics · Physics 2021-01-07 Maximilian Mörchen , Leon Freitag , Markus Reiher

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

In this article we study the effects of higher body excitations in the relativistic CC calculations for atoms and ions with one valence electron using Fock-space CCSD, CCSD(T) and its unitary variants. The present study demonstrates that…

Atomic Physics · Physics 2009-11-13 Chiranjib Sur , Rajat K Chaudhuri

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

For noncovalent interactions, it is generally assumed that CCSD(T) is nearly the exact solution within the 1-particle basis set. For the S66 noncovalent interactions benchmark, we present for the majority of species CCSDT and CCSDT(Q)…

Chemical Physics · Physics 2025-01-22 Emmanouil Semidalas , A. Daniel Boese , Jan M. L. Martin

Coupled-cluster theory with single and double excitations (CCSD) is a promising ab initio method for the electronic structure of three-dimensional metals, for which second-order perturbation theory (MP2) diverges in the thermodynamic limit.…

Materials Science · Physics 2021-06-16 James M. Callahan , Malte F. Lange , Timothy C. Berkelbach

We have studied electron correlations in the doped two-dimensional (2D) Hubbard model by using the coupled-cluster method (CCM) to investigate whether or not the method can be applied to correct the independent particle approximations…

Strongly Correlated Electrons · Physics 2009-10-31 Yoshihiro Asai , Hideki Katagiri

Basis set convergence of correlation effects on molecular atomization energies beyond the CCSD (coupled cluster with singles and doubles) approximation has been studied near the one-particle basis set limit. Quasiperturbative connected…

Chemical Physics · Physics 2008-08-17 Amir Karton , Peter R. Taylor , Jan M. L. Martin

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

Obtaining sub-chemical accuracy (1 kJ mol${}^{-1}$) for reaction energies of medium-sized gas-phase molecules is a longstanding challenge in the field of thermochemical modeling. The perturbative triples correction to CCSD, CCSD(T),…

Chemical Physics · Physics 2025-03-26 Tingting Zhao , James H. Thorpe , Devin A. Matthews

One method of representing a high-rank tensor as a (hyper-)product of lower-rank tensors is the tensor hypercontraction (THC) method of Hohenstein et al. This strategy has been found to be useful for reducing the polynomial scaling of…

Chemical Physics · Physics 2025-03-26 Avdhoot Datar , Devin A. Matthews

While restricted single-reference coupled cluster theory truncated to singles and doubles (CCSD) provides very accurate results for weakly correlated systems, it usually fails in the presence of static or strong correlation. This failure is…

Chemical Physics · Physics 2016-02-25 Ireneusz W. Bulik , Thomas M. Henderson , Gustavo E. Scuseria

A full coupled-cluster expansion suitable for sparse algebraic operations is developed by expanding the commutators of the Baker-Campbell-Hausdorff series explicitly for cluster operators in binary representations. A full coupled-cluster…

Chemical Physics · Physics 2018-09-13 Enhua Xu , Motoyuki Uejima , Seiichiro L. Ten-no

A practical high-accuracy relativistic method of atomic structure calculations for univalent atoms is presented. The method is rooted in the coupled-cluster formalism and includes non-perturbative treatment of single and double excitations…

Atomic Physics · Physics 2009-11-11 Sergey G. Porsev , Andrei Derevianko

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

An electrodynamical coupled cluster (CC) methodology starting from a covariant formalism and an equal time approximation, and finally based on the Dirac-Fock picture of the electron and positron fields and Coulomb gauge, is given here. The…

Atomic Physics · Physics 2019-04-30 Sambhu N. Datta

We implement the Fock-space perturbed relativistic coupled-cluster theory to compute the electric dipole polarizability of ground and low lying excited states, and nuclear spin-dependent parity violating (NSD-PNC) transition amplitudes in…

Atomic Physics · Physics 2024-12-17 Suraj Pandey , Ravi Kumar , D. Angom , B. K. Mani

The relative energies of different phases or polymorphs of molecular solids can be small, less than a kiloJoule/mol. Reliable description of such energy differences requires high quality treatment of electron correlations, typically beyond…

Chemical Physics · Physics 2024-02-19 Khanh Ngoc Pham , Marcin Modrzejewski , Jiří Klimeš

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

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