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We present the theoretical framework, implementation, and benchmark results for a reduced-cost relativistic equation-of-motion coupled cluster singles and doubles (EOM-CCSD) method based on state-specific frozen natural spinors (SS-FNS). In…

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

We present a natural orbital-based implementation of the intermediate Hamiltonian Fock space coupled-cluster method for (1,1) sector of Fock space. The use of natural orbital significantly reduces the computational cost and can…

Chemical Physics · Physics 2021-09-07 Soumi Haldar , Achintya Kumar Dutta

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

We present the theory and the implementation of a low-cost four-component relativistic equation of motion coupled cluster method for ionized states based on frozen natural spinors. A single threshold (natural spinor occupancy) can control…

Chemical Physics · Physics 2024-06-19 Kshitijkumar Surjuse , Somesh Chamoli , Malaya K. Nayak , Achintya Kumar Dutta

We have developed a reduced-cost non-Dyson third-order algebraic diagrammatic construction theory for the electron-attachment problem based on state-specific frozen natural orbitals. Density fitting and truncated natural auxiliary functions…

Chemical Physics · Physics 2026-03-13 Tamoghna Mukhopadhyay , Kamal Majee , Achintya Kumar Dutta

In this work, we present frozen natural orbital (FNO) based implementations of equation-of-motion (EOM) coupled-cluster (CC) with singles, doubles, and triples (SDT) for ionization potential (IP), double ionization potential (DIP), electron…

Chemical Physics · Physics 2025-09-18 Manisha , Prashant Uday Manohar

The equation of motion coupled cluster singles and doubles model (EOM-CCSD) is an accurate, black-box correlated electronic structure approach to investigate electronically excited states and electron attachment or detachment processes. It…

Chemical Physics · Physics 2023-09-18 Loïc Halbert , Andre Severo Pereira Gomes

We introduce a new equation-of-motion coupled-cluster method based on a pair coupled-cluster doubles (pCCD) reference, termed frozen-pair EOM-CCSD (EOM-fpCCSD). This approach combines the computational efficiency of the pCCD ansatz with a…

Chemical Physics · Physics 2026-05-06 Katharina Boguslawski , Paweł Tecmer

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…

The accurate description of doubly-excited states using conventional electronic structure methods is remarkably challenging, primarily because such excited states require the inclusion of doubly or higher excited configurations or the…

Chemical Physics · Physics 2019-05-01 Katharina Boguslawski

In this work we describe the rank-reduced variant of the equation-of-motion coupled cluster theory with complete inclusion of single, double, and triple excitations. The advantage of the proposed formalism in comparison with the canonical…

Chemical Physics · Physics 2026-05-15 Piotr Michalak , Michał Lesiuk

We present the coupled-cluster singles and doubles method formulated in terms of truncated pair-natural orbitals (PNO) that are optimized to minimize the effect of truncation. Compared to the standard ground-state PNO coupled-cluster…

Chemical Physics · Physics 2020-06-09 Marjory C. Clement , Jinmei Zhang , Cannada A. Lewis , Chao Yang , Edward F. Valeev

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

We report the implementation of equation-of-motion coupled-cluster (EOMCC) method in the four-component relativistic framework with the spherical atomic potential to generate the excited states from a closed-shell atomic configuration. This…

Atomic Physics · Physics 2015-06-19 D. K. Nandy , Yashpal Singh , B. K. Sahoo

Excited-state methods within the nuclear--electronic orbital (NEO) framework have the potential to capture vibrational, electronic, and vibronic transitions in a single calculation. In the NEO approach, specified nuclei, typically protons,…

Chemical Physics · Physics 2026-03-16 Jonathan H. Fetherolf , Fabijan Pavošević , Sharon Hammes-Schiffer

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 present a computationally efficient relativistic formulation of the equation-of-motion coupled-cluster method for the double electron attachment problem. In this work, the exact two-component Hamiltonian within the atomic mean-field…

Chemical Physics · Physics 2026-03-31 Sujan Mandal , Tamoghna Mukhopadhyay , Achintya Kumar Dutta

We show that by working in a basis similar to that of the natural transition orbitals and using a modified zeroth order Hamiltonian, the cost of a recently-introduced perturbative correction to excited state mean field theory can be reduced…

Chemical Physics · Physics 2020-09-03 Rachel Clune , Jacqueline A. R. Shea , Eric Neuscamman

The projection-based quantum embedding method is applied to electronically excited states of valence, Rydberg, and charge-transfer character, valence- and core-ionized states, as well as bound and temporary radical anions. We embed…

Chemical Physics · Physics 2021-06-10 Valentina Parravicini , Thomas-C. Jagau
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