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We report in this paper an implementation of 4-component relativistic Hamiltonian based Equation-of-Motion Coupled-Cluster with singles and doubles (EOM-CCSD) theory for the calculation of ionization potential (IP), electron affinity (EA)…

Chemical Physics · Physics 2018-11-09 Avijit Shee , Trond Saue , Lucas Visscher , Andre Severo Pereira Gomes

Density functional theory (DFT) is a widespread and effective tool in electronic structure calculations for ground-state electron systems. Its success has prompted exploration into the use of DFT for non-collective excited states. The delta…

Chemical Physics · Physics 2025-08-12 Ethan Pollack , Rohan Maniar , John P. Perdew

We present a modification of the $\Delta$SCF method of calculating energies of excited states, in order to make it applicable to resonance calculations of molecules adsorbed on metal surfaces, where the molecular orbitals are highly…

Materials Science · Physics 2009-03-06 Jeppe Gavnholt , Thomas Olsen , Mads Engelund , Jakob Schiøtz

The dual exponential coupled cluster (CC) theory proposed by Tribedi et al.[J. Chem. Theory Comput. 2020, 16, 10, 6317-6328] performs significantly better than the coupled cluster theory with singles and doubles excitations (CCSD) due to…

Computational Physics · Physics 2023-07-26 Anish Chakraborty , Rahul Maitra

We extend our recently-developed heat-bath configuration interaction (HCI) algorithm, and our semistochastic algorithm for performing multireference perturbation theory, to the calculation of excited-state wavefunctions and energies. We…

Strongly Correlated Electrons · Physics 2017-11-22 Adam A. Holmes , C. J. Umrigar , Sandeep Sharma

We show that, as in Hartree Fock theory, the orbitals for excited state mean field theory can be optimized via a self-consistent one-electron equation in which electron-electron repulsion is accounted for through mean field operators. In…

Chemical Physics · Physics 2020-12-02 Tarini S. Hardikar , Eric Neuscamman

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…

A systematic method for determining correlated wavefunctions of extended systems in the ground and excited states is presented. It allows to fully exploit the power of quantum-chemical programs designed for correlation calculations of…

Other Condensed Matter · Physics 2007-05-23 V. Bezugly

Recently developed pair coupled cluster doubles (pCCD) theory successfully reproduces doubly occupied configuration interaction (DOCI) with mean field cost. However, the projective nature of pCCD makes the method non-variational and thus…

Chemical Physics · Physics 2016-08-19 Luning Zhao , Eric Neuscamman

The coupled cluster method (CCM) has previously been applied to study the ground- and excited-state properties of many different types of frustrated and unfrustrated quantum spin systems. A common feature in the application of the CCM is to…

Strongly Correlated Electrons · Physics 2014-02-20 Damian J. J. Farnell , Andrew I. Croudace

In quantum chemistry, obtaining a system's mean-field solution and incorporating electron correlation in a post Hartree-Fock (HF) manner comprise one of the standard protocols for ground-state calculations. In principle, this scheme can…

Chemical Physics · Physics 2020-09-02 Hong-Zhou Ye , Troy Van Voorhis

A balanced description of ground and excited states is essential for the description of many chemical processes. However, few methods can handle cases where static correlation is present, and often these scale very unfavourably with system…

Chemical Physics · Physics 2019-05-08 Hugh G. A. Burton , Alex J. W. Thom

Molecular ground-state simulation is one of the most promising fields for demonstrating practical quantum advantage on near-term quantum computers. However, the Variational Quantum Eigensolver (VQE), a leading algorithm for this task, still…

Quantum Physics · Physics 2025-07-08 Runhong He , Qiaozhen Chai , Xin Hong , Ji Guan , Guolong Cui , Shengbin Wang , Shenggang Ying

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

An efficient excited state method, named xCDFCI, in the configuration interaction framework, is proposed. xCDFCI extends the unconstrained nonconvex optimization problem in coordinate descent full configuration interaction~(CDFCI) to a…

Chemical Physics · Physics 2023-08-23 Zhe Wang , Zhiyuan Zhang , Jianfeng Lu , Yingzhou Li

The pair-coupled-cluster doubles (pCCD) method has emerged as a viable approach for quantum-chemical studies of strongly correlated systems. Despite its lower formal scaling (O(N$^4$)) compared to other versions of coupled cluster (CC)…

Chemical Physics · Physics 2026-04-17 Rahul Chakraborty , Paweł Tecmer

In a recent paper [JCTC, 2020, 16, 6098], we introduced a new approach for accurately approximating full CI ground states in large electronic active-spaces, called Tensor Product Selected CI (TPSCI). In TPSCI, a large orbital active space…

Chemical Physics · Physics 2023-08-07 Nicole M. Braunscheidel , Vibin Abraham , Nicholas J. Mayhall

State-specific electronic structure theory provides a route towards balanced excited-state wave functions by exploiting higher-energy stationary points of the electronic energy. Multiconfigurational wave function approximations can describe…

Chemical Physics · Physics 2023-07-19 Antoine Marie , Hugh G. A. Burton

The ground-state correlation energy calculated in the random-phase approximation (RPA) is known to be identical to that calculated using a subset of terms appearing in coupled-cluster theory with double excitations. In particular, this…

Chemical Physics · Physics 2019-04-16 Timothy C. Berkelbach

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…

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