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We generalize the Aufbau suppressed coupled cluster formalism into the realm of doubly excited states by deriving, implementing, and testing a wave function initialization strategy that allows the zeroth order wave function to match the…

Chemical Physics · Physics 2026-05-11 Qasim Javed , Harrison Tuckman , Eric Neuscamman

The phenomenon of orbital relaxation upon excitation of core electrons is a major problem in the linear-response treatment of core-hole spectroscopies. Rather than addressing relaxation through direct dynamical correlation of the excited…

Chemical Physics · Physics 2025-03-26 Megan Simons , Devin A. Matthews

In the framework of the computational determination of highly-accurate vertical excitation energies in small organic compounds, we explore the possibilities offered by the equation-of-motion formalism relying on the approximate fourth-order…

Striving to define very accurate vertical transition energies, we perform both high-level coupled cluster (CC) calculations (up to CCSDTQP) and selected configuration interaction (sCI) calculations (up to several millions of determinants)…

We present excitation energies for molecular doublets from a spin-adapted formulation of coupled cluster singles and doubles theory. The entanglement coupled cluster approach represents an unconventional take on the notorious problem of…

Chemical Physics · Physics 2025-04-08 Sarai Dery Folkestad , Kristine Lauvstad Kruken , Henrik Koch

Excited states exhibiting double excitation character are notoriously difficult to model using conventional single-reference methods, such as adiabatic time-dependent density-functional theory (TD-DFT) or equation-of-motion coupled cluster…

We present a linear-response formulation of density cumulant theory (DCT) that provides a balanced and accurate description of many electronic states simultaneously. In the original DCT formulation, only information about a single…

Chemical Physics · Physics 2018-09-10 Andreas V. Copan , Alexander Yu. Sokolov

The similarity transformed equation of motion coupled cluster (STEOM-CC) method is benchmarked against CC3 and EOM-CCSDT-3 for a large test set of valence excited states of organic molecules studied by Schreiber et al. [M. Schreiber, M.R.…

Chemical Physics · Physics 2018-01-09 J. Sous , P. Goel , M. Nooijen

A major difficulty in quantum simulation is the adequate treatment of a large collection of entangled particles, synonymous with electron correlation in electronic structure theory, with coupled cluster (CC) theory being the leading…

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

In this work, we revisited the idea of using the coupled-cluster ground state formalism to target excited states. Our main focus was targeting doubly excited states and double core hole states. Typical equation-of-motion (EOM) approaches…

Chemical Physics · Physics 2019-12-04 Joonho Lee , David W. Small , Martin Head-Gordon

Inspired by our earlier semi-stochastic work aimed at converging high-level coupled-cluster (CC) energetics [J. E. Deustua, J. Shen, and P. Piecuch, Phys. Rev. Lett. 119, 223003 (2017); J. Chem. Phys. 154, 124103 (2021)], we propose a novel…

Chemical Physics · Physics 2022-10-06 Karthik Gururangan , J. Emiliano Deustua , Jun Shen , Piotr Piecuch

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

We present a novel and cost-effective approach of using a second similarity transformation of the Hamiltonian to include the missing higher-order terms in the second-order approximate coupled cluster singles and doubles (CC2) model. The…

Chemical Physics · Physics 2022-01-26 Soumi Haldar , Achintya Kumar Dutta

A novel approach to rapidly converging high-level coupled-cluster (CC) energetics in an automated fashion is proposed. The key idea is an adaptive selection of the excitation manifolds defining higher-than-two-body components of the cluster…

Chemical Physics · Physics 2023-08-25 Karthik Gururangan , Piotr Piecuch

An externally corrected coupled cluster (CC) method, where an adaptive configuration interaction (ACI) wave function provides the external cluster amplitudes, named ACI-CC, is presented. By exploiting the connection between configuration…

Chemical Physics · Physics 2023-09-27 Gustavo J. R. Aroeira , Madeline M. Davis , Justin M. Turney , Henry F. Schaefer

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

We explore the possibility of calculating electronic excited states by using perturbation theory along a range-separated adiabatic connection. Starting from the energies of a partially interacting Hamiltonian, a first-order correction is…

Chemical Physics · Physics 2014-12-15 Elisa Rebolini , Julien Toulouse , Andrew M. Teale , Trygve Helgaker , Andreas Savin

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 present a novel theoretical scheme for orbital relaxation in configuration interaction singles (CIS) based on a perturbative treatment of its electronic Hessian, whose analytical derivation is also established in this work. The proposed…

Chemical Physics · Physics 2026-03-06 Takashi Tsuchimochi

We present a comprehensive theoretical study of the physical phenomena that determine the relative energies of the three of the lowest electronic states of each of the square-planar copper complexes $\cucl$, $\cunh$ and $\cuwater$, and…

Strongly Correlated Electrons · Physics 2018-06-14 Emmanuel Giner , David Tew , Yann Garniron , Ali Alavi