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We introduce an approach to improve single-reference coupled cluster theory in settings where the Aufbau determinant is absent from or plays only a small role in the true wave function. Using a de-excitation operator that can be efficiently…

Chemical Physics · Physics 2024-07-03 Harrison Tuckman , Eric Neuscamman

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

Modeling charge transfer well can require treating post-excitation orbital relaxations and handling medium to large molecules in realistic environments. By combining a state-specific correlation treatment with such orbital relaxations,…

Chemical Physics · Physics 2025-07-28 Harrison Tuckman , Eric Neuscamman

We investigate the ability of Aufbau suppressed coupled cluster theory to act as a post-linear-response correction to widely used linear response methods for electronically excited states. We find that the theory is highly resilient to…

Chemical Physics · Physics 2025-06-23 Trine Kay Quady , Harrison Tuckman , Eric Neuscamman

We present an excited-state-specific coupled-cluster approach in which both the molecular orbitals and cluster amplitudes are optimized for an individual excited state. The theory is formulated via a pseudoprojection of the traditional…

Chemical Physics · Physics 2023-11-27 Harrison Tuckman , Eric Neuscamman

A new state specific correlation correction to configuration interaction singles (CIS) excitation energies is preseted using coupled cluster perturbation theory (CCPT). General expressions for CIS-CCPT are derived and expanded explicitly to…

Chemical Physics · Physics 2015-06-19 Jason N. Byrd , Victor F. Lotrich , Rodney J. Bartlett

We derived and implemented the calculation of the one-body reduced density matrix for Aufbau suppressed coupled cluster theory, from which excited state natural orbitals and one-body properties, like atomic populations and dipole moments,…

Chemical Physics · Physics 2026-03-20 Conor Bready , Harrison Tuckman , Eric Neuscamman

The (T) and [T] perturbative corrections are derived for multicomponent coupled-cluster theory with single and double excitations (CCSD). Benchmarking shows that multicomponent CCSD methods that include the perturbative corrections are more…

Chemical Physics · Physics 2022-07-01 Dylan Fowler , Kurt R. Brorsen

We introduce perturbation and coupled-cluster theories based on a cluster mean-field reference for describing the ground state of strongly-correlated spin systems. In cluster mean-field, the ground state wavefunction is written as a simple…

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

This work presents a first time accurate calculation of the magnetic dipole hyperfine structure constants for the ground state and some low-lying excited states of Pb$^+$. By comparing different levels of approximation with experimental…

Atomic Physics · Physics 2009-11-10 Bijaya K. Sahoo , Rajat K. Chaudhuri , B. P. Das , Holger Merlitz , Debashis Mukherjee

Cluster perturbation theory is a technique for calculating the spectral weight of Hubbard models of strongly correlated electrons, which combines exact diagonalizations on small clusters with strong-coupling perturbation theory at leading…

Strongly Correlated Electrons · Physics 2009-11-07 D. Sénéchal , D. Pérez , D. Plouffe

We investigate the use of perturbation theory in finite sized frustrated spin systems by calculating the effect of quantum fluctuations on coherent states derived from the classical ground state. We first calculate the ground and first…

Strongly Correlated Electrons · Physics 2009-10-31 N. P. Konstantinidis , D. Coffey

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

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

We develop a cubic scaling approach to excited-state-specific second order perturbation theory in which the completeness of a local correlation treatment is carefully matched between the ground and excited state. With this matching, the…

Chemical Physics · Physics 2025-05-14 Rachel Clune , Eric Neuscamman

We employ the closed-shell perturbed relativistic coupled-cluster (RCC) theory developed by us earlier [Phys. Rev. A {\bf 77}, 062516 (2008)] to evaluate the ground state static electric dipole polarizabilities (\alpha s) of several atomic…

Atomic Physics · Physics 2013-12-09 Yashpal Singh , B. K. Sahoo , B. P. Das

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

We propose a streamlined combination scheme of the transcorrelation (TC) and coupled cluster (CC) theory, which not only increases the convergence rate with respect to the basis set, but also extends the applicability of the lowest order CC…

Strongly Correlated Electrons · Physics 2021-07-28 Ke Liao , Thomas Schraivogel , Hongjun Luo , Daniel Kats , Ali Alavi

The Coupled-Cluster theory is one of the most successful high precision methods used to solve the stationary Schr\"odinger equation. In this article, we address the mathematical foundation of this theory with focus on the advances made in…

Chemical Physics · Physics 2019-09-04 Andre Laestadius , Fabian M. Faulstich
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