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The study of isolated defects in solids is a natural target for classical or quantum embedding methods that treat the defect at a high level of theory and the rest of the solid at a lower level of theory. Here, in the context of…

Materials Science · Physics 2023-01-25 Bryan T. G. Lau , Brian Busemeyer , Timothy C. Berkelbach

The exploration of the root structure of coupled cluster equations holds both foundational and practical significance for computational quantum chemistry. This study provides insight into the intricate root structures of these non-linear…

Chemical Physics · Physics 2024-09-12 Svala Sverrisdóttir , Fabian M. Faulstich

We present an ab initio study of electronically excited states of three-dimensional solids using Gaussian-based periodic equation-of-motion coupled-cluster theory with single and double excitations (EOM-CCSD). The explicit use of…

Materials Science · Physics 2020-01-31 Xiao Wang , Timothy C. Berkelbach

A reduced-complexity variant of equation-of-motion coupled-cluster singles and doubles (EOM-CCSD) method is formulated in terms of state-averaged excited state pair natural orbitals (PNO) designed to describe manifolds of excited states.…

Chemical Physics · Physics 2020-06-09 Chong Peng , Marjory C. Clement , Edward F. Valeev

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…

A new perturbative approach to canonical equation-of-motion coupled-cluster theory is presented using coupled-cluster perturbation theory. A second-order M{\o}ller-Plesset partitioning of the Hamiltonian is used to obtain the well known…

Chemical Physics · Physics 2015-07-09 Jason N. Byrd , Varun Rishi , Ajith Perera , Rodney J. Bartlett

We extend the CIPSI-driven CC($P$;$Q$) methodology [K. Gururangan et al., J. Chem. Phys. 155 (2021) 174114], in which the leading higher-than-doubly excited determinants are identified using the selected configuration interaction (CI)…

Chemical Physics · Physics 2026-02-24 Swati S. Priyadarsini , Karthik Gururangan , Piotr Piecuch

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

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

By combining extrapolated selected configuration interaction (sCI) energies obtained with the CIPSI (Configuration Interaction using a Perturbative Selection made Iteratively) algorithm with the recently proposed short-range…

Chemical Physics · Physics 2020-06-05 Emmanuel Giner , Anthony Scemama , Julien Toulouse , Pierre-François Loos

Cyclobutadiene is a well-known playground for theoretical chemists and is particularly suitable to test ground- and excited-state methods. Indeed, due to its high spatial symmetry, especially at the $D_{4h}$ square geometry but also in the…

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

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

Fourth-order many-body corrections to matrix elements for atoms with one valence electron are derived. The obtained diagrams are classified using coupled-cluster-inspired separation into contributions from n-particle excitations from the…

Atomic Physics · Physics 2009-11-07 Andrei Derevianko , Erik D. Emmons

The calculation of molecular excited states is critically important to decipher a plethora of molecular properties. In this manuscript, we develop an equation of motion formalism on top of a bi-exponentially parametrized ground state…

Chemical Physics · Physics 2024-01-09 Anish Chakraborty , Pradipta Kumar Samanta , Rahul Maitra

The accurate computation of excited states remains a challenge in electronic structure theory, especially for systems with a ground state that requires a multireference treatment. In this work, we introduce a novel equation-of-motion (EOM)…

Chemical Physics · Physics 2025-05-28 Shuhang Li , Zijun Zhao , Francesco A. Evangelista

We revisit here the lowest vertical excitations of cyanine dyes using quantum Monte Carlo and leverage on recent developments to systematically improve on previous results. In particular, we employ a protocol for the construction of compact…

Chemical Physics · Physics 2021-11-22 Alice Cuzzocrea , Saverio Moroni , Anthony Scemama , Claudia Filippi

Accurate yet efficient modeling of chemical systems with pronounced static correlation in their excited states remains a significant challenge in quantum chemistry, as most electronic structure methods that can adequately capture static…

Chemical Physics · Physics 2025-03-07 Sylvia J. Bintrim , Kevin Carter-Fenk

We present a coupled cluster method (CCM) with optimized excitation operators. The efficiency comes from a parameterized form of excitation operators. The parameters are found by variational optimization procedure. The resultant number of…

Strongly Correlated Electrons · Physics 2014-12-09 Quanlin Jie

We investigate the accuracies of different coupled cluster levels in a finite model solid, the 14 electron spin-non-polarised uniform electron gas. For densities between $\mathrm{r}_\mathrm{s}$ = 0.5 $\mathrm{a}_\mathrm{0}$ and…

Chemical Physics · Physics 2018-03-28 Verena A. Neufeld , Alex J. W. Thom