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We discuss the analytic and diagrammatic structure of ionization potential (IP) and electron affinity (EA) equation-of-motion coupled-cluster (EOM-CC) theory, in order to put it on equal footing with the prevalent $GW$ approximation. The…

Chemical Physics · Physics 2019-04-16 Malte F. Lange , Timothy C. Berkelbach

We investigate the convergence of coupled-cluster correlation energies and related quantities with respect to the employed basis set size for the uniform electron gas to gain a better understanding of the basis set incompleteness error. To…

Materials Science · Physics 2024-02-27 Nikolaos Masios , Felix Hummel , Andreas Grüneis , Andreas Irmler

We combine the electron attachment (EA) and ionization potential (IP) equation-of-motion (EOM) coupled-cluster (CC) approaches with the CC($P$;$Q$) formalism. The resulting methodologies are used to describe the electronic states of several…

Chemical Physics · Physics 2025-09-19 Karthik Gururangan , Stephen H. Yuwono , A. Eugene DePrince , Piotr Piecuch

We describe further details of the Stochastic Coupled Cluster method and a diagnostic of such calculations, the shoulder height, akin to the plateau found in Full Configuration Interaction Quantum Monte Carlo. We describe an initiator…

Chemical Physics · Physics 2016-03-23 James S. Spencer , Alex J. W. Thom

New stochastic approaches for the computation of electronic excitations are developed within the many-body perturbation theory. Three approximations to the electronic self-energy are considered: $G_0W_0$, $G_0W_0^tc$, and…

Chemical Physics · Physics 2019-08-27 Vojtech Vlcek

We report an implementation of the core-valence separation approach to the 4-component relativistic Hamiltonian based equation-of-motion coupled-cluster with singles and doubles theory (CVS-EOM-CCSD), for the calculation of relativistic…

Coupled-cluster (CC) theory and Green's function many-body perturbation theory (MBPT) have long evolved as distinct yet complementary frameworks for describing electronic correlation. While CC methods employ exponential wavefunction…

We present a variational Monte Carlo algorithm for estimating the lowest excited states of a quantum system which is a natural generalization of the estimation of ground states. The method has no free parameters and requires no explicit…

Computational Physics · Physics 2024-09-04 David Pfau , Simon Axelrod , Halvard Sutterud , Ingrid von Glehn , James S. Spencer

The prediction of electronic structure for strongly correlated molecules represents a promising application for near-term quantum computers. Significant attention has been paid to ground state wavefunctions, but excited states of molecules…

Quantum Physics · Physics 2025-01-08 Harper R. Grimsley , Francesco A. Evangelista

Wavefunctions restricted to electron pair states are promising models for strongly-correlated systems. Specifically, the pair Coupled Cluster Doubles (pCCD) ansatz allows us to accurately describe bond dissociation processes and…

Strongly Correlated Electrons · Physics 2019-05-01 Katharina Boguslawski

We consider a fermionic system for which there exist a single-reference configuration-interaction (CI) expansion of the ground state wave function that converges, albeit not necessarily rapidly, with respect to excitation number. We show…

Strongly Correlated Electrons · Physics 2020-01-13 Dominic Bergeron

Problems in quantum chemical simulations, especially achieving accurate excited-state potential energy surfaces, are among the primary applications to achieve quantum utility. On near-term quantum hardware, variants of the variational…

The double ionization potential (DIP) equation-of-motion (EOM) coupled-cluster (CC) method with 4-hole--2-particle (4$h$-2$p$) excitations on top of the CC with singles, doubles, and triples calculation, abbreviated as…

We are proposing a new computational thermochemistry protocol denoted W3 theory, as a successor to W1 and W2 theory proposed earlier [Martin and De Oliveira, J. Chem. Phys. 111, 1843 (1999)]. The new method is both more accurate overall…

Chemical Physics · Physics 2007-05-23 A. Daniel Boese , Mikhal Oren , Onur Atasoylu , Jan M. L. Martin , Mihaly Kallay , Juergen Gauss

While limited coupled cluster theory is \textit{formally} nonvariational, it is not broadly appreciated whether this is a major issue \textit{in practice}. We carried out a detailed comparison with \textit{de facto} full CI energies for a…

Chemical Physics · Physics 2024-10-03 Jan M. L. Martin , Emmanouil Semidalas

We extend our assessment of the potential of perturbative coupled cluster (CC) expansions for a test set of open-shell atoms and organic radicals to the description of quadruple excitations. Namely, the second- through sixth-order models of…

Chemical Physics · Physics 2016-05-17 Janus J. Eriksen , Devin A. Matthews , Poul Jørgensen , Jürgen Gauss

We introduce a unitary coupled-cluster (UCC) ansatz termed $k$-UpCCGSD that is based on a family of sparse generalized doubles (D) operators which provides an affordable and systematically improvable unitary coupled-cluster wavefunction…

Quantum Physics · Physics 2019-01-07 Joonho Lee , William J. Huggins , Martin Head-Gordon , K. Birgitta Whaley

Unitary Coupled Cluster (UCC) theory is a promising variational method for electronic structure calculations, especially for strongly correlated systems and quantum computers. However, its practical application is limited by the steep…

Chemical Physics · Physics 2026-02-05 Prateek Vaish , Brenda Rubenstein

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

Based on 280 reference vertical transition energies of various natures (singlet, triplet, valence, Rydberg, $n\to\pi^*$, $\pi\to\pi^*$, and double excitations) extracted from the QUEST database, we assess the accuracy of third-order…

Chemical Physics · Physics 2022-07-04 Martial Boggio-Pasqua , Denis Jacquemin , Pierre-François Loos